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The enthalpies of solid solutions La2-xSrxCuO4−δ (0≤x(Sr)≤1.2) formation were determined from thermochemical study using hermetic swinging isoperibolic calorimeter at 298.15 K and the Gibbs energies were estimated. It was found that the solid solutions in La2CuO4 – Sr2CuO3 system are thermodynamically unstable at x(Sr)>0.6.