Acquisition of highly accurate energetic data for chromium-containing molecules and various chromium carbonyl complexes is a major step toward calibrating bond energies and thermal isomerization energies from mechanisms for Cr-centered photochromic materials being developed in our laboratories. The performance of six density functionals in conjunction with seven basis sets, utilizing Gaussian-type orbitals, has been evaluated for the calculation of gas-phase enthalpies of formation and enthalpies of reaction at 298.15 K on various chromium-containing systems. Nineteen molecules were examined: Cr(CO)(6), Cr(CO)(5), Cr(CO)(5)(C2H4), Cr(CO)(5)(C2C1H3), Cr(CO)(5)(cis-(C2Cl2H2)), Cr(CO)5(gem-(C2Cl2H2)), Cr(CO)(5)(trans-(C2Cl2H2)), Cr(CO)(5)(C2Cl3H), Cr(CO)(5)(C2Cl4), CrO2, CrF2, CrCl2, CrCl4, CrBr2, CrBr4, CrOCl2, CrO2Cl2, CrOF2, and CrO2F2. The performance of 69 density functionals in conjunction with a single basis set utilizing Slater-type orbitals (STO) and a zeroth-order relativistic approximation was also evaluated for the same test set. Values derived from density functional theory were compared to experimental values where available, or values derived from the correlation consistent composite approach (ccCA). When all reactions were considered, the functionals that exhibited the smallest mean absolute deviations (MADs, in kcal mol(-1)) from ccCA-derived values were B97-1 (6.9), VS98 (9.0), and KCIS (9.4) in conjunction with quadruple-C STO basis sets and B97-1 (9.3) in conjunction with cc-pVTZ basis sets. When considering only the set of gas-phase reaction enthalpies (Delta H-r degrees(gas),), the functional that exhibited the smallest MADs from ccCA-derived values were B97-1 in conjunction with cc-pVTZ basis sets (9.1) and PBEPBE in conjunction with polarized valence triple-zeta basis set/effective core potential combination for Cr and augmented and multiple polarized triple-C Pople style basis sets (9.5). Also of interest, certainly because of known cancellation of errors, PBEPBE with the least-computationally expensive basis set combination considered in the present study (valence double-zeta basis set/effective core potential combination for Cr and singly-polarized double-C Pople style basis sets) also provided reasonable accuracy (11.1). An increase in basis set size was found to have an improvement in accuracy for the best performing functional (B97-1).