Solution combustion synthesis (SCS) is shown to be versatile for the rapid-one-pot synthesis of three compounds and four polymorphs in the Cu−V−O ternary family: α-CuV 2 O 6 , αand β-Cu 2 V 2 O 7 , and γ-Cu 3 V 2 O 8. These compounds feature copper/vanadium stoichiometric ratios ranging from 1:1 to 3:1; their structural, electronic, optoelectronic, and photoelectrochemical attributes were comprehensively characterized by a combination of theoretical and experimental techniques. The main contribution of the present study is the demonstration that a range of stoichiometries in this compound family can be derived simply by tuning the precursor mole ratio in the SCS procedure. The Cu−V−O family of samples, derived by SCS, is shown to exemplify the strong effect of compound stoichiometry on the optoelectronic and photoelectrochemical properties. Overall, α-CuV 2 O 6 showed the best performance, rooted in the direct nature of the optical transition in this material. Finally, SCS is very timeefficient and the various compositions can be obtained in a matter of minutes, as opposed to hours or even days in classical solution-based or ceramic synthesis routes.