Five new polymers based on the 4,4′-difluoro-4-bora-3a,4a-diaza-s-indacene core (BODIPY) chromophore moiety have been synthesized as low bandgap polymers for optoelectronic applications. The polymers exhibited high solubility in common organic solvents and optical bandgaps ranging from 1.7–2 eV. The materials were characterized using NMR, UV-Vis, steady state and time-resolved photoluminescence and the energy levels were examined using electrochemistry and validated using quantum chemical calculations. Finally, a representative BODIPY derivative : PCBM blend was examined in terms of photovoltaic properties. Preliminary device performance parameters as a function of photo-active layer thickness and composition are reported and discussed, relating to power conversion efficiency values.