α-Cyano-3-methoxy-4-hydroxycinnamic acid（CFA）was applied in analysis of the synthesized polymer A and B by matrix-assisted laser desorption/ionization time of flight mass spectrometry（MALDI-TOF-MS）.The results showed that CFA can exhibit an excellent matrix function,compared with the common matrices（e.g.DHB,HCCA,SA and DIT） in terms of resolution and signal-to-noise of the obtained mass spectra.The information of the relative molecular mass,molecular weight distribution and constitutional repeating unit of polymer A and B were obtained,which will be instructive to the optimization of polymer reaction conditions and the speculation of reaction mechanism.