Effects of Ce substitution at the A-site of LaNi0.5Fe0.5O3 perovskite on the enhanced catalytic activity for dry reforming of methane (DRIVI) were studied. La1-xCexNi0.5Fe0.5O3 mixed-oxide catalyst precursors were synthesized by a sol-gel self-combustion method. The CH4 and CO2 conversions increase for the samples with x = 0.4-0.6. The used catalysts consist of Ni, CeO2, and (LaCe)(NiFe)O-3. The metallic Ni phase provides the primary catalytic activity, while (LaCe)(NiFe)O-3 perovskite dominates the enhanced catalytic activity. It is confirmed that the solubility of Ce in the perovskite is high under the DRM conditions. Our results suggest that the Ce3+ cation at the A-site of (LaCe)(NiFe)O-3 is active for DRM, and the relevant mechanisms are discussed.