Solid phase coordination reaction of Sm3+ and the resultant of the imidization of polycondensor of polycondensation and imidization of benzoguanamine(BGA) and 2, 4-tolylenediisocyanate (TDI) and pyromellitic dianhydride (PMIDA) under microwave irradiation were synthesized and studied. The effect of microwave irradiation time (power), the composition of reactants and the reaction temperature on the yield and Sm content in complexes were studied. The complex was determined by Fourier transform infrared absorption (FTIR), Fourier transform Roman spectrum (FTRS), scanning electric minor (SEM), 13C solid state nuclear magnetic resonance spectrometry and X-ray powder diffraction. The fluorescence intensity was measured by fluorescent emission spectrum and compared with thermal coordination. The magnetic susceptibilities were measured by magnetic curve. The results showed that the complex had not characteristic fluorescence of Sm3+, which illustrated that the first excitation level of Sm3+ and polymer could not match at all. But the complex showed good magnetic property of the ion.