The parameters of the tensor of the electric field gradient (EFG) in cation sites of the La2 − xSrxCuO4 lattice have been determined by the method of emission Mossbauer spectroscopy on 57Co(57mFe), 67Cu(67Zn), 67Ga(67Zn), and 155Eu(155Gd) isotopes. There is no quantitative agreement between the calculated (the pointcharge model) and experimental values of the main component of the tensor EFG Vzz, which is explained by the absence of the reliable data on the Sternheimer coefficients for Fe3+, Zn2+, and Gd3+ ions. Based on the comparison of the calculated and experimental dependences of Vzz on x it was shown that the holes appearing during the substitution of La3+ for Sr2+ are localized preferably on the oxygen atoms that are in the same plane as the copper atoms, which is in agreement with the model discussed in the literature and assumes that the mechanism responsible for the high-temperature superconductivity of solid solutions La2 − xSrxCuO4 is the interaction between the conductivity electrons and two-atomic two-electron centers with negative correlation energy.