To enhance the visible photo-catalytic activity of TiO2, La/V co-doped TiO2 materials were synthesized through a nonaqueous method of which the purpose was to reduce the aggregation between TiO2 particles. Different samples of La and V co-doped TiO2 nanoparticles were prepared through simple sol–gel synthesis method by using Vanadium(III) chloride as V precursor, Lanthanum(III) chloride heptahydrate as La precursor, and titanium (IV) butoxide (TBT) as titanium precursor. The effects of co-doping content on the structural, optical, and photo-catalytic properties of nanoparticles have been studied by X-ray diffraction (XRD), TEM, SEM and UV–Vis absorption spectroscopy. XRD results suggest that adding impurities has a great effect on the crystallinity and particle size of TiO2. Titania rutile phase formation in ternary system (Ti–La–V) was inhibited by La3+ and promoted by V4+ co-doped TiO2 in high concentration of vanadium and 22.6 mol% anatase composition is retained at 15% vanadium. The photocatalyst activity was evaluated by photocatalytic degradation kinetics of aqueous methylen orange under visible radiation. The results show that the photocatalytic activity of the 10 mol% V and 5 mol% La co-doped TiO2 nanopowders has a larger