Abstract Substitution of Na, K, Rb, and Sr for La in the perovskite type structure complex oxide LaMnO 3 were carried out and their structure and properties were investigated. Lattice symmetry of the samples sintered at 1393 K in O 2 gas flow was found to be rhombohedral. Rietveld refinement to X-ray diffraction data revealed a systematic decrease of the lattice distortion with substitution. The change of temperature dependence of resistivity from semiconducting to metallic and the increase of the ferromagnetic transition temperature with substitution were recognized and found to be closely related to structural changes. The anomalies in the Seebeck coefficient at the ferromagnetic transition temperature suggest a strong correlation between the electronic state and magnetism.