Single-crystal-like TiO2 is claimed to be a very promising material among various catalysts. In this study, the (N,F)-co-doped single-crystal-like TiO2 was prepared by a new molten mixing process in which the mixed nitrates were used both as a morphology modifier and an N-doping agent at the same time. The prepared samples also had well-developed (001) facet due to the addition of HF. The HF can also be an F doping agent to the material. The co-doping of N and F can diminish the band gap of TiO2 from 3.05 to 2.93 eV, therefore visible light can be used effectively by the material. In addition, NO and fluorine ions existing on the surface of the sample can also help its photocatalyticity. Therefore, the photocatalytic performance of the as-prepared sample was effectively improved.