To overcome the drawback of poor solar light utilization brought about by the narrow photoresponse range of TiO2, a silver and sulfur co-doped TiO2 was synthesized. Using the prepared catalyst, solar photocatalytic degradation of 2-nitrophenol (2-NP) by a TiO2-based catalyst was studied for the first time. Effects of the co-doping on the structural, optical and morphological properties of the synthesized nanoparticles were investigated by different characterization methods: X-ray diffraction, N2 adsorption–desorption measurements, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, UV–visible diffuse reflectance spectroscopy and Fourier transform infrared spectroscopy. Solar experiments showed that the co-doping with silver and sulfur significantly increased the photocatalytic activity. In various initial concentrations of 2-NP more than 99% of the contaminant was decomposed by Ag-S/TiO2 in less than 150 minutes, while the degradation efficiency was much less in the presence of bare TiO2. Kinetic studies suggested that solar photocatalytic degradation of 2-NP is consistent with the Langmuir–Hinshelwood model. The rate constant of the reaction and adsorption constant of the modified photocatalyst were found to be 2.4 and 4.1 times larger than that of bare TiO2, respectively.