Matrix assisted laser desorption/ionization time of flight mass spectrometry（MALDI-TOF MS） is a new kind of soft ionization bio mass spectrometry，which has been rapidly developed in the past decade.It plays an important role in the analysis of small molecule compounds.The selection of matrix has always been the focus of researchers′ attention.At present，a variety of new MALDI-TOF MS matrixes have been developed，which could be divided into two major categories：nanomaterials and new organic compounds.The improvement of matrixes properties makes MALDI-TOF MS work with higher accuracy and sensitivity，smaller background noise，and cleaner spectra.Nevertheless，many reports are still at the research stage，and the traditional organic matrixes still could not be replaced at this stage.In this paper，the research progress of the new matrixes is sorted out，the advantages，characteristics and applicable objects of different types of matrixes are summarized.and the research future of matrixes for MALDI-TOF MS is prospected.