A gas chromatography－negative chemical ionization－mass spectrometry（GC－NCI－MS） with derivatization was developed for the quantitative analysis of nitrite（NO,${\mathrm{2}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248093&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248092&type=,1.10066664,3.72533321,） and nitrate（NO,${\mathrm{3}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248103&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248100&type=,1.10066664,3.72533321,） in whole blood. Isotope-labeled ,15,NO,${\mathrm{2}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248093&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248092&type=,1.10066664,3.72533321, and ,15,NO,${\mathrm{3}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248082&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248081&type=,1.10066664,3.72533321, were used as the internal standards．After NO,${\mathrm{2}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248093&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248092&type=,1.10066664,3.72533321, and NO,${\mathrm{3}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248090&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248089&type=,1.10066664,3.72533321, in whole blood were extracted and derivatized，the target derivatives were analyzed by GC－NCI－MS. The target extraction solvent，derivative extraction solvent，amount of phase transfer reagent，the derivatization method，time and temperature of the derivatization reaction were optimized．The optimal pretreatment conditions were also determined．A negative chemical ionization source（NCI） was used to select ion monitor（SIM）．The quantitative ions for target NO,${\mathrm{2}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248093&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248092&type=,1.10066664,3.72533321, and its internal standard ,15,NO,${\mathrm{2}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248098&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248095&type=,1.10066664,3.72533321, were ,m,/,z, 46 and 47，while those for target NO,${\mathrm{3}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248103&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248100&type=,1.10066664,3.72533321, and its internal standard ,15,NO,${\mathrm{3}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248112&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248107&type=,1.10066664,3.72533321, were ,m,/,z, 62 and 63，respectively．There was a good linear relationship for NO,${\mathrm{2}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248122&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248117&type=,1.10066664,3.72533321, in whole blood（,r,2, = 0.995） in the range of 0.05－5 μg/mL，with a detection limit of 0.01 μg/mL and an accuracy of 89.6%－98.0%．The extraction recoveries ranged from 99.8% to 118%，with the intra-day and inter-day relative standard deviations（RSDs） of 1.8%－9.2% and 2.1%－6.2%，respectively．There also existed a good linear relationship for NO,${\mathrm{3}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248129&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248126&type=,1.10066664,3.72533321, in whole blood（,r,2, = 0.997） in the range of 1－300 μg/mL，with a detection limit of 0.2 μg/mL and an accuracy of 92.8%－112%．The extraction recoveries ranged from 80.3% to 88.4%，with the intra-day and inter-day RSDs of 0.60%－14% and 0.60%－3.7%，respectively. The endogenous NO,${\mathrm{2}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248135&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248132&type=,1.10066664,3.72533321, and NO,${\mathrm{3}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248142&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248139&type=,1.10066664,3.72533321, in 16 whole blood samples of healthy person were determined by this method．The results showed that the concentrations of NO,${\mathrm{2}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248151&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248145&type=,1.10066664,3.72533321, and NO,${\mathrm{3}-}_{}^{}$,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248160&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37248157&type=,1.10066664,3.72533321, were in the ranges of 0.05－0.10 μg/mL and 1.70－7.70 μg/mL，respectively．In addition，the contents of two target substances in real human whole blood poisoned by nitrite were determined，and the concentrations of both substances were much higher than the endogenous concentration level in whole blood of human body，thus nitrite poisoning was determined．With the advantages of strong specificity，high sensitivity，accuracy and reliability，the method could meet the requirements for inspection and identification of nitrite poison cases．