A new poly(N-allyl-tetrasubstituted imidazole) containing furan rings and benzene ring was synthesized starting from 1-allyl-4,5-di(furan-2-yl)-2-phenyl-1H-imidazole (N-allyl-tetrasubstituted imidazole, monomer) using benzoyl peroxide as an initiator coupled with the mixture of benzene and water as solvents. The influence factors on the conversion of N-allyl-tetrasubstituted imidazole (monomer) were optimized by the orthogonal experiment. The structure and property of the obtained monomer and polymers were characterized by Fourier infrared spectroscopy, high-resolution mass spectroscopy, nuclear magnetic resonance spectroscopy, X-ray diffraction, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. Moreover, the luminescence property of monomer and polymers from the different polymerization conditions was investigated. The results showed that the luminescence property and thermal stability of polymer were related to molecular weight and the crystallization degree of polymer, and their thermal stability was markedly better than monomer. It suggested that poly(N-allyl-tetrasubstituted imidazole) had potential application in the fields of heat-resistant material and luminescence material.