A number of compounds, which correspond to composition of La1-3xLixSr2xCoO3-ѓВ (0.x.0,33;) have been synthesized. Limits of existence of solid solutions in the La . Li . Sr . Co . O system were found using XR analysis, concentration dependencies of crystal lattice parameters on substitution degree have been plotted. The correlation between a value of oxygen nonstoichiometry and structure characteristics of the oxide materials has been found. Their electro physical properties were investigated.