Although many materials display the transition from insulating to metallic behavior on doping, only a few, such as VO 2 , have the right combination of crystal structure and physical properties to serve as model systems.Here we report the electronic and structural characteristics of the insulator to metal transition in V 1−x Mo x O 2 , which we have studied over the range 0.0Յ x Յ 0.50 through characterization of the electrical resistivity, magnetic susceptibility, specific heat, and average-and short-range crystal structures. We find that metal-metal pairing exists in small domains in the doped metallic phases and an unexpected phenomenology for the crossover between a Curie-Weiss insulating regime and an intermediate mass metallic regime. An electronic phase diagram is presented.