We report the synthesis of Sr1-xCaxMnO3 and La0.5Ba0.5MnO3 perovskites over extended cation and oxygen composition ranges and describe the dependence of their phase stability on the tolerance factor t = t(x,T,σ) that is a function of composition, temperature, and oxygen content. We show that magnetic transition temperatures depend strongly on the tolerance factor and charge disorder while dependence on the structural disorder is less important. By reducing charge and structural disorder we have significantly increased the Curie and Neel temperatures for perovskite manganites.