A series of poly(pentafluorophenyl (methyl)acrylates)-block-poly(ethylene oxide) with o-nitrobenzyl ester photocleavable junctions (PPFP(M)A-hv-PEO) were synthesized by RAFT polymerization. The block copolymers were used to fabricate thin films and fibers by spin-coating and electrospinning, respectively. After solvent annealing, UV exposure, and washing with methanol/water to remove the minor PEO block, nanoporous structures were obtained. Both the porous thin films and fibers remained reactive to amine substitution of the pentafluorophenyl esters under mild conditions, which was confirmed by XPS, fluorescence confocal microscopy, FT-IR, and contact angle measurements.