The electronic structure of the single-crystalline solid solutions Nb1-xVxSe2 has been studied using soft X-ray photoelectron, resonant photoelectron, and absorption spectroscopy. A charge transfer between VSe2 and NbSe2 sublattices was observed. This charge transfer makes the octahedral coordination of the Nb atoms by Se atoms preferable as compared to the trigonal-prismatic coordination in undoped NbSe2.