A quantum-mechanical potential barrier model for estimating the number ratio between different valence cations in multiatom compounds is proposed. It is supposed that there is a potential barrier between a cation-anion pair. The height of the potential barrier is proportional to the ionization energy of the cation, and the width of the potential barrier is related to the distance between neighboring cations and anions. As examples for using this model, the distribution of cations with different valences in some ABO3 lanthanum manganites is explained satisfactorily.