Perovskite-based catalysts with a self-regeneration property, named intelligent catalysts, were developed for CH4 partial oxidation, and the effect of redox treatment on regeneration behavior of the catalytic activity was investigated. Rh-substituted catalysts such as LaM0.95Rh0.05O3 (M: Cr, Co, Fe) were prepared by the Pechini method. Among the catalysts, LaCr0.95Rh0.05O3 exhibited the highest and the most stable catalytic activity for partial oxidation of methane before and after redox treatment. The precipitation and dissolution of Rh species were confirmed by X-ray photoelectron microscopy and transmission electron microscopy, indicating that the catalyst regenerated itself via the redox process.