Abstract The effect of cerium substitution on the electrical and electrochemical characteristics of a new anode material La 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3 (LSCM) was examined by synthesizing Ce x La 0.75– x Sr 0.25 Cr 0.5 Mn 0.5 O 3 for x = 0–0.375). From x = 0–0.25, the structure is rhombohedral (S.G. R‐3c), and with a higher cerium content ( x = 0.375) it becomes cubic (S.G. Pm‐3m). These materials are stable in the operating conditions of an SOFC anode. Ce x La 0.75– x Sr 0.25 Cr 0.5 Mn 0.5 O 3 and LSCM materials are p‐type semi‐conductors. Cerium substitution improves the conductivity in neutral atmosphere from 18.3 to 35.4 S cm –1 for x = 0 and 0.375, respectively, at 1,173 K. In reducing conditions, the conductivity is not influenced by cerium substitution, and it is about 1 S cm –1 at 1,173 K. High temperature XRD shows that structure becomes cubic at 1,073 K in operating (reducing) conditions. Cerium substitution positively enhances the electrochemical behavior, as proved by studying the properties of dense cone‐shaped electrodes.