The synthesis of a series of novel, unsymmetrically substituted benzothiadiazole-containing vinyl monomers and their free radical polymerization with and without the control of a reversible addition-fragmentation chain transfer (RAFT) agent is reported. The resulting polymers with electroactive pendants show tunable absorption and emission spectra depending on their molecular architecture. Using RAFT allows the synthesis of block copolymers using a hole-transporting vinyl-triarylamine as a second monomer. Efficient energy transfer between the two pendants has been detected. Cyclic voltammetry and photoelectron spectroscopy in air measurements have been employed to reveal the location of the HOMO and LUMO of the block copolymers. The block copolymers also influence the morphology of spin-casted films and show rectifying behavior in organic photovoltaic devices.