TiV-oxide photocatalysts were synthesized through sol–gel technique for different Ti:V ratio. They were characterized using XRD, SEM, EDAX, UV-Vis-DRS, photoluminescence, and FTIR studies. The systems with high Ti:V ratio showed a mixed phase while with low ratio a rutile phase. The sizes of the particles were between 20 and 30 nm showing an increase with change in phase from mixed to rutile. The reflectance spectrum showed a red-shift in the optical response covering a large portion of visible spectrum.Interestingly, both mixed and rutile phases showed visible light activity in the photodegradation of methylene blue under laboratory conditions. However,mixed-phase catalyst showed high activity in terms of rate of degradation and photonic efficiency.