Abstract: Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) has irreplaceable advantages in the characterization of synthetic polymers, and provides information on the mass distribution, block length and end groups of polymers. However, sample preparation is critical for successful analysis because of the poor ionization efficiency of synthetic polymers. The research progress on sample preparation of synthetic polymers analyzed by MALDI-TOF was reviewed from three aspects: matrix, matrix additives and sample mixing methods.