In polycrystalline air-fired perovskites of Ca((1-x))(La)(x)TiO3 Stoichiometry (x = 0.00-0.15), the positron annihilation lifetime increased monotonically with x, and showed an similar to 40% increase of the lifetime at xsimilar to0.1, at which value the lifetime increase saturated. These data, together with measured perovskite stoichiometry, indicate that equal numbers of Ca and Ti vacancies were the prime charge compensators. Thermal gravimetric data are consistent with charge compensation occurring via the cation vacancies in the air-fired samples and Ti3+ in equivalent samples prepared under reducing conditions.