Modern telecommunications require materials with high dielectric constants (κ). The number of suitable elements ultimately limits one approach to the discovery of new materials, targeting compositions with high atomic polarizabilities (α). By decreasing the molar volume of compositions with high α, however, we anticipated dramatic increases in κ and demonstrated that this approach works. The quenched high-pressure perovskite polymorph of Na2MTeO6 (M = Ti, Sn) showed a twofold increase in κ, compared to the ilmenite form. This result suggested the highest values of κ occur for compositions with high α, which form quenchable compounds at high pressures and temperatures.