Abstract <p>The paper presents curves of potential energy and dipole moments for the X²Π ground state and low-lying A²Σ⁺ and B²Π excited states of the CaO⁺ ion. They were plotted using multiconfiguration methods of electronic structure calculation subject to spin-orbit interaction. Electron-vibrational-rotational spectra caused by spontaneous transitions between vibrational-rotational levels of the X²Π, A²Σ⁺, and B²Π electronic states of the CaO⁺ cation were synthesized on their basis. The calculation results can be used for simulating the optical cooling of the CaO⁺ molecular ion.</p>