Three stable polyradicals with large π-conjugated planar phenalenyl (PLY) radical units as side chain were synthesized. Due to the different conjugated backbones and the interactions between main chains and side chains, these polyradicals and their corresponding precursor polymers presented diverse optical and electrical properties, which were confirmed by UV–vis, fluorescence and CV detections. Besides, they showed excellent solubility in common organic solvents and good stability in the air. Considering their special characteristics, we have fabricated photovoltaic (PV) devices using these polyradicals or polymers as donor material and PCBM as acceptor material. The significant PV performance improvement was observed using a radical-based active layer in the PV devices.