The photovoltaic property of Rhodamine B dye embedded into Poly(tolyl-1,1'-binaphthyl carbamate) (PU(1)) and poly(hexamethylene-1,1'-binaphthyl carbamate) (PU(2)) matrices have been evaluated using host-guest approach. The photoactive layer comprising photoluminescent polymer matrix (PU(1) or PU(2)), Rhodamine B and TiO(2) nanoparticles were prepared by spin casting method. The power conversion efficiency (PCE) the photovoltaic devices based on PU(1) and PU(2) matrices were found to be 0.043% and 0.029%, respectively. PCE of the photovoltaic devices were limited due to low lying highest occupied molecular orbital of PU(1) and PU(2) polymers. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 122: 3316-3321, 2011