Using first principles density functional calculations, we here connect the physical properties of binderless tungsten carbides with the theoretical electronic structure as calculated from density functional theory calculations. We show that electronic structure calculations predict and explain various known phenomena in these systems, an example of how such theoretical studies can be a valuable tool in materials science. For example, changes in the energy of formation from 25% substitution with Mo or Ti is used to explain the differences in intermixing between binderless tungsten carbides using TiC or Mo2C as γ binder phase. Substitutions with Ti atoms are also predicted to stabilize tungsten carbide in the NaCl-structure. A study of the charge density redistribution after substitution is also made.