Phase equilibria, crystal structure, and transport properties in the (100−x) La0.95Ni0.6Fe0.4O3–xCeO2 (LNFCx) system (x=2–75 mol%) were studied in air. Evolution of phase compositions and crystal structure of components was observed. The LNFCx (2≤x≤10) are three-phase and comprise the perovskite phase with rhombohedral symmetry (R3̄c), the modified ceria with fluorite structure (Fm3̄m), and NiO as a secondary phase. These multiphase compositions exhibit metallic-like conductivity above 300 °C. Their conductivity gradually decreases from 395.6 to 260.6 S/cm, whereas the activation energy remains the same (Ea=0.04–0.05 eV), implying the decrease in the concentration of charge carriers. Phase compositions in the LNFCx (25≤x≤75) are more complicated. A change from semiconducting to metallic-like conductivity behavior was observed in LNFC25 at about 550 °C. The conductivity of LNFCx (25≤x≤75) could be explained in terms of a modified simple mixture model.