Organic reference materials（RMs） have been widely used in the spectrum analysis fields.The certified techniques for chemical purity of organic RMs are key factors for the certification of RMs.One kind of the certification techniquec for organic RMs is the direct method，which can give the certified value by measuring the main component.The direct methods include gas chromatography（GC），liquid chromatography（LC），quantity nuclear magnetic resonance（qNMR），elemental analysis（EA） and titration method（mass titration and volumetric titration）.The other one is the indirect method，which certify the value by substracting the impurities from the total content，such as freezing point depression（FPD），differential scanning calorimetry（DSC），coupled with water determination，residual solvent measurement and inorganic impurities determination.This paper summarized the certification methods for organic RMs with high purity（2000-2011），compared the advantages and disadvantages of these techniques,and also gave an outlook for the development of certification method for organic RMs in the future.