Data on search for correlations between a structure of state diagrams of binary systems based on V-Me (Me = Ti, Zr, Hf, Nb, Ta, Cr, Mo, W) and crystal-geometric and crystal-chemical parameters were presented. Manifestation of both positive and negative deviations in experimental concentration dependences of the atomic volume in solid solutions in systems V-Me (Me = Ti, Nb, Ta, Cr, Mo) from Zen’s law was established. It was found that in the systems with unbounded regions of solid solutions, the deviation from Zen’s law is insignificant. A correlation was found between the types of state diagrams and the difference in atomic volumes of alloy-forming elements in systems V-Me (Me = Ti, Nb, Ta, Cr, Mo).