La0.7-xCexSr0.3MnO3 specimens were fabricated by a solid state reaction method and structural and electrical properties with variation of Ce4+ contents were measured. All specimens exhibited a polycrystalline rhombohedral crystal structure, and the (110) peaks were shifted to low angle side with increasing the amount of Ce4+ contents. As Ce4+ ions with different ion radii and charges are substituted with La3+ ions, electrical properties are thought to be affected by changes in the double exchange interaction between Mn3+-Mn4+ ions due to distortion of the unit lattice, a decrease in oxygen vacancy concentration, and an increase in lattice defects. Resistivity gradually decrease as the amount of Ce4+ added increased, and negative temperature coefficient of resistance (NTCR) properties were shown in all specimens. In the La0.5Ce0.2Sr0.3MnO3 specimens, electrical resistivity, TCR and B-value were 31.8 Ω-cm, 0.55%/℃ and 605 K, respectively.