Photo-crosslinkable PF-b-PCEA triblock copolymers have been successfully synthesized by an end-capped Yamamoto reaction and further atom transfer radical polymerization. The copolymer film on a glass substrate could be selectively photo-crosslinked using 365 nm UV radiation and a mask with a standard photopattern process. Elaborate and complex pixel structures are easily obtained, which may be applied to fabricate pixelated matrix displays and large area displays in the future. Furthermore, the crosslinked PF-b-PCEA film shows better stability under thermal stress and UV irradiation than the homopolymer, which indicates that the block copolymers could have a longer lifetime and stability when they are used in OLED fabrication. The optical properties and conversion of the photo-responsive group are also investigated by various methods and confirm the photo-responsive property. The corresponding results show that many other types of photo-crosslinkable light-emitting materials can be conveniently and efficiently obtained by this method.