Wide-light absorption is important to semiconductors exploited in many applications such as photocatalysts, photovoltaic devices, and light-emitting diodes, which can effectively improve solar energy utilization. Especially for photocatalysts, the development and design of new semiconductors that harvest the whole-visible-light region (λ = 400-800 nm) is rarely reported, which is still a tremendous challenge up to now. Here we realize whole-visible-light absorption up to 900 nm for a semiconductor by means of construction of a mixed-valence Ag0.68V2O5, which results from an assistant effect of d-d transition. Ag0.68V2O5 serving as a photocatalyst obviously exhibits photoelectrochemical and photocatalytic properties. Our results provide a brand-new feasible design strategy to broaden the light absorption of semiconductors and highlight a route to further make the best use of the full solar spectrum.