The paper presents the results of research on the influence of sintering temperature on microstructure, DC electrical conductivity, dielectric, ferroelectric and magnetic properties of PbFe1/2Nb1/2O3 ceramics doped by Li in the amount of 5.0% wt., in the abbreviation PLiFN. The ceramic samples of the PLiFN material were obtained by the two-stage synthesis – columbite method and sintered by free sintering methods. Introduction to the basic PbFe1/2Nb1/2O3 composition of the lithium admixture to decrease the electrical conductivity and reduction of dielectric loss. The tests have shown that the increase in sintering temperature orders the PLiFN ceramic microstructure, which has a positive effect on its electrophysical properties. At room temperature, the PLiFN ceramic samples show both ferroelectric and ferromagnetic properties. Considering the functional parameters of the obtained ceramic samples, the optimal technological conditions are 1100°C/2 h.