We present X-ray photoelectron, Co $${{L}_{{2,3}}}$$ and O K X-ray absorption, as well as Co $$K{{\beta }_{{1,3}}}$$ X-ray emission spectroscopy results of studies of the spin states of trivalent cobalt ions in single-crystal cobaltite LaCoO₃. We show that at room temperature, in the bulk of a LaCoO₃ single crystal, Co³⁺ ions are in the low-spin state, while high-spin Co²⁺, high-spin Co³⁺, low-spin Co³⁺, and probably also intermediate-spin Co³⁺ ions are located on the surface.