The performance of La 2−x Ce x Cu 1−y Zn y O 4 perovskites as catalysts for the high temperature water-gas shift reaction (HT-WGSR) was investigated. The catalysts were characterized by EDS, XRD, BET surface area, TPR, and XANES. The results showed that all the perovskites exhibited the La 2 CuO 4 orthorhombic structure, so the Pechini method is suitable for the preparation of pure perovskite. However, the La 1.90 Ce 0.10 CuO 4 perovskite alone, when calcined at 350/700 °C, also showed a (La 0.935 Ce 0.065 ) 2 CuO 4 perovskite with tetragonal structure, which produced a surface area higher than the other perovskites. The perovskites that exhibited the best catalytic performance were those calcined at 350/700 °C and, among these, La 1.90 Ce 0.10 CuO 4 was outstanding, probably because of the high surface area associated with the presence of the (La 0.935 Ce 0.065 ) 2 CuO 4 perovskite with tetragonal structure and orthorhombic La 2 CuO 4 phase.