Abstract: This paper briefly introduces the development, basic principles , main advantages and disadvantages , and difficult in analysis of synthetic polymers by matrix assisted laser desorption/ion-ization time-of-flight mass spectrometry. And also discuss the effect of matrix, solvent, cation-ization salt, and sample preparation technique, critical factors on the experiment results and the cause of mass discrimination. This paper also elucidates the application and future of MALDI ? TOF MS in analysis of synthetic polymers such as homopolymers, blends and copolymers.