Surface functionalized poly(ethylene-co-methacrylic acid) (PE-co-MAA) nanofibrous membranes were successfully prepared and applied as solid supports to immobilize photosensitizers. Several activation agents were used to facilitate the surface functionalization of PE-co-MAA nanofibrous membranes, and PCl 5 was found to be the most efficient one to activate surface carboxylic acid groups. Three spacers with variable lengths were introduced to the membrane surfaces prior to immobilizations of protoporphyrin IX (PPIX), a photosensitizer. The results revealed that the membranes with longer spacer chain incorporated more photoactive macrocyclic compounds, and the supported PPIX provided a more powerful catalytic effect on the photo-oxidation of 1,5-dihydroxynaphthalene. After five times of repeated catalytic reactions, the catalytic activity of the solid supported PPIX was maintained at 80% of the original power, and the membrane morphology was intact. The nanofibrous membrane supported photosensitizer provided high catalytic activity, easy handling, good durability and reusability.