New polyimine derivative containing fluorene group in the main chain was synthesized via Suzuki cross-coupling polymerization, reduction, and imine formation reaction, consecutively. The synthesized polymer was characterized and explored as organic photovoltaic cell device. The imine polymer P3 in diluted chloroform solution emitted red light (582 nm), whereas its precursor polymers P1 and P2 showed green (about 530 nm) and blue fluorescence (477 nm), respectively. Bulk heterojunction photovoltaic cells fabricated by blending P3 with the fullerene derivative PCBM was found to have a power conversion efficiency of upto 0.0005%, while cells from blending P3 with MEH-PPV yielded 0.0008% of power conversion efficiency.