Series of Mn2.3Co3.7 ZnxCuyO4 (x=0, 0.03, 0.06; y=0, 0.05, 0.08, 0.1, 0.2) were used as negative-temperature-coefficient (NTC) thermistor. The microstructure and electrical properties of the samples were studied by EDS, SEM and FTIR. The results indicate that series of Mn-Co-O NTC ceramics with the relatively low electrical resistivity and high B constant were obtained by adding ZnO, CuO, when the x=0.03, y=0.05 led to the desired electrical parameters. The added Zn+ cations have a strong tendency to place themselves on the octahedral sites of the spinel lattice and lead to an increase in electrical resistivity and the B constant, but Cu2+ ions occupy both octahedral and tetrahedral sites and cause an decrease in those parameters. At the same time, we find that segregation of CuO occur at the grain boundary.