The wide interest in developing green energy technologies stimulates the scientific community to seek, for devices, new substitute material platforms with low environmental impact, ease of production and processing and long-term stability. The synthesis of metal oxide (MO) semiconductors fulfils these requirements and efforts are addressed at optimizing their functional properties, through improvement of charge mobility or energy level alignment. Two MOs have rising perspectives for application in light harvesting devices, mainly for the role of charge selective layers but also as light absorbers, namely MoO3 (an electron blocking layer) and Co3O4 (a small band gap semiconductor). The need to achieve better charge transport has prompted us to attempt doping strategies with vanadium (V) ions that, when combined with oxygen in V2O5, produce a high work function MO. We report on subcritical hydrothermal synthesis of V-doped mesostructures of MoO3 and of Co3O4, in which a tight control of the doping is exerted by tuning the relative amounts of reactants. We accomplished a full analytical characterization of these V-doped MOs that unambiguously demonstrates incorporation of the vanadium ions in the MO crystal lattice, as well as effects on the optical properties and work function. We foresee a promising future use of these materials as charge selective materials in energy devices based on multilayer structures.