Photochromic and photoluminescence materials show bright colors under different excitation conditions, and thus, these functional materials have been applied in many fields. Based on the photochromic and photoluminescence theories, a block copolymer, which could be directly processed into nanofibers by electrospinning, was successfully prepared through atom transfer radical polymerization ( ATRP ) . To synthesize the block copolymer, a vinyl monomer containing a spiropyran unit was employed to prepare the photochromic chain segment, and a polymethyl methacrylate ( PMMA) chain segment was introduced to improve the processability of the block copolymer. Acting as the photoluminescence unit, the rare earth complex was linked to the side chain through coordination bonding between the rare earth ions and the ester groups of PMMA. When the photochromic and photoluminescence block copolymer was exposed to different wavelengths of ultraviolet ( UV ) light and visible ( Vis ) light, it could show white, red, green, yellow, and blue-purple. These results provide the potential of the as-prepared photochromic and photoluminescence block copolymer for application in fibers and fabrics.