Polylactide-b-fullerene-b-poly(3-hexylthiophene) (PLA-b-C-60-b-P3HT) triblock copolymer via a combination of 1,3-dipolar cycloaddition reaction and controlled ring-opening polymerization technique was successfully synthesized. The structure, morphology and crystallinity of PLA-b-C-60-b-P3HT copolymer were characterized by H-1 NMR, GPC, DSC, TGA, XRD, UV-vis, PL and AFM measurements. Nanoporous C-60/P3HT films were easily prepared from PLA-b-C-60-b-P3HT triblock copolymer by casting the copolymer followed by thermal annealing and chemical etching of the PLA chains. Fullerene molecules could self-assembly between P3HT and PLA to form a continuous film. An ordered nanoporous C-60/P3HT film was formed in AFM by chemically etching the PLA microphase with NaOH solution. Photoluminescence analysis showed that the photoinduced electron transfer of the ordered nanoporous C-60/P3HT film was significantly improved compared to the physically blending sample due to the increased interface between the P3HT and the C-60.