A photoswitchable nanomaterial is presented, electrospun organic nanofibers based on 1',3'-dihydro-1',3',3'-trimethyl-6-nitrospiro [2H-1-benzopyran-2,2'-(2H)-indole]. The switching properties of the nanofibers were investigated by studying the evolution of absorbance with different UV exposure times, photoluminescence lifetime, cyclic photoisomerization, and reversible wettability. The unique potentialities of photoswitchable nanofibers for achieving enhanced control of surface wettability are shown.