The transition energies to the low-lying singlet and triplet excited states of Cr(CO)₆ are computed by equation-of-motion coupled cluster singles and doubles (EOM-CCSD) and similarity transformed equation-of-motion coupled cluster singles and doubles (STEOM-CCSD) methods with all-electrons basis sets. Both experimental and optimized geometries are used for the calculations. Calculations with various basis sets, among them one of the largest calculations performed at the EOM-CCSD level, based on atomic natural orbitals with 627 functions, were used to evaluate the basis set influence on computed transition energies. The presence of a shoulder at 3.9 eV in the experimental absorption spectrum, assigned to the ¹A_1g → ¹T_2u transition, which was not reproduced by recent density functional theory (DFT) or multi-state complete active space perturbation theory (MS-CASPT2) is supported by the present STEOM-CCSD calculations with a theoretical value of 3.92 eV. In addition to this weak ¹A_1g → a ¹T_2u absorption, we observe two strong absorptions corresponding to ¹A_1g → a ¹T_1u at 4.37 eV (vs. an experimental value of 4.46 eV) and ¹A_1g → b ¹T_1u at 5.20 eV (vs. an experimental value of 5.53 eV). Both are characterized as metal-to-ligand charge-transfer (MLCT) allowed transitions. The first metal-centered (MC) absorption at 4.37 eV in our best calculation is degenerate with the lowest MLCT absorbing state. The one-dimensional potential energy curves associated to the low-lying singlet MLCT and MC states as a function of the chromium axial carbonyl bond distance q_a = [Cr–CO_axial] show that an avoided crossing exists between the a ¹T_1g (MC) and a ¹T_1u (MLCT) states near 1.92 Å, which is very close to the equilibrium Cr–CO distance. Moreover, the MC state seems to be dissociative for the CO loss. These two important features could explain the ultra-fast dissociation of CO (100 fs) observed in recent low intensity laser probed gas phase experiments.