A facile method to prepare nanofibrous ZnO photoelectrodes with tunable thicknesses by electrospinning is reported. A "self-relaxation layer" is formed spontaneously between ZnO nanofibers and fluorine-doped SnO2 (FTO) substrate, which facilitates the release of interfacial tensile stress during calcination, resulting in good adhesion of ZnO film to FTO substrate. Dye-sensitized solar cells (DSSCs) based on the nanofibrous ZnO photoelectrodes are fabricated and an energy conversion efficiency of 3.02% is achieved under irradiation of AM 1.5 simulated sunlight with a power density of 100 mW cm(-2), which shows good promise of electrospun nanofibrous ZnO as the photoelectrode in DSSCs.