The electron and positron charge densities are calculated as a function of position in the unit cell for the Hg1–xCdxTe alloy system using the empirical pseudopotential method combined with the virtual‐crystal approximation. The results show that the positron has a strong affinity to one sort of atoms in binary semiconductors. The results of the positron charge density should provide valuable insight into the effect of annihilation. The electron charge density and the ionicity character with respect to the variation of the mole fraction are discussed.