The electronic structure of VxMo1-x (x=0.2; 0.4; 0.6; 0.75) solid solutions was studied by XPS and UPS. The density of states at the Fermi energy, N(EF), deduced from these measurements, shows a minimum as a function of the alloy concentration on the Mo rich side. This behaviour can be explained by band structure calculations and is in good agreement with previous NMR measurements. The relation between the electronic structure at the Fermi level and the superconducting properties is discussed. The band structure of the Mo rich alloys can be understood in terms of a rigid band model. © 1985 Springer-Verlag.