The synthesis of a poly(1,3-dithienylisothianaphthene) (PDTITN) derivative obtained via oxidative polymerization of 5,6-dichloro-1,2-bis(3‘-dodecylthienyl)isothianaphthene is described. PDTITN exhibits a band gap of 1.80-1.85 eV. The redox properties of PDTITN were characterized using cyclic voltammetry and spectroelectrochemisty. Photoexcitation of PDTITN results in photoluminescence (PL) in the near-IR region and the formation of a triplet state. In the presence of a methanofullerene (PCBM) as an electron acceptor, PL and triplet formation of PDTITN are quenched. In photovoltaic devices using blends of the polymer with PCBM, the observed incident-photon-to-collected-electron efficiency (IPCE) up to 24% at 400 nm and the 3 orders of magnitude increase of short circuit current as compared to the polymer alone prove the photoactivity of the PDTITN/PCBM blend in the device.