The photovoltaic property of Rhodamine B dye embedded into Poly(tolyl-1,1′-binaphthyl carbamate) (PU1) and poly(hexamethylene-1,1′-binaphthyl carbamate) (PU2) matrices have been evaluated using host-guest approach. The photoactive layer comprising photoluminescent polymer matrix (PU1 or PU2), Rhodamine B and TiO2 nanoparticles were prepared by spin casting method. The power conversion efficiency (PCE) the photovoltaic devices based on PU1 and PU2 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 PU1 and PU2 polymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.