Conjugated polyacetylenes having pendant fullerene and/or porphyrin groups were prepared by copolymerization in the presence of [Rh(nbd)Cl](2)-NEt3 in CHCl3. The photochemical and electrochemical properties of the polymers were studied by UV-vis spectroscopy and voltammetry. The photoinduced charge-transfer properties of the monolayer films were also measured by a three-electrode cell technique. More importantly, poly(1a(0.2)-co-5(0.8)) shows a high capacity to form a photoinduced charge-separated state and to produce steady and prompt photocurrent at the irradiation of 21.2 mW cm(-2) white light. We estimate an aerobic IPCE value of 0.15% for a true monolayer coverage of poly(1a(0.2)-co-5(0.8)) at its peak absorption around 440 nm (the maximum of the Soret band).