Nanoporous zirconia electrospun fiber mats (NZEFM) have been prepared by an electrospinning process using nonionic F108 as a pore-forming agent. This nonaqueous synthesis route has been employed to fabricate a stable “building block” porous structure inside the nano-scale fibers. The mats composed of individual fibers proved to be robust after calcination at up to 450°C or stirring in water. The photocatalytic activity of NZEFM is apparently higher than that of commercial zirconia powder for the degradation of methyl orange in aqueous solution. Moreover, amorphous NZEFM mixed with the tetragonal phase obtained at 450°C proved to be more efficient than the monoclinic phase NZEFM obtained at 900°C. Various dyes could be degraded by NZEFM under UV light irradiation. The highly photocatalytic activity of NZEFM could be attributed to its high specific surface area and nanoporous “building block” structure made up of stacked zirconia nanoparticles.