Communication: Polymerization of a functionalized acetylene was successfully performed using a Rh complex as the catalyst and triethylamine as a base yielding poly{(EEE)-4-[4-[4-(3,4,5-tridodecyloxystyryl)-2,5-bis((S)-2-methylbutoxy)styryl]-2,5-bis((S)-2-methylbutoxy)styryl]phenylacetylene } (PAOPV). Films of PAOPV mixed with a fullerene derivative showed electron transfer from the OPV oligomer donor to the fullerene acceptor. The films could be furthermore used in photovoltaic devices.