The resolved structure of the lowest-energy oxo to osmium charge-transfer absorption band of trans-[OsO2(malonate)(2)](2-) is analyzed on the basis of the exact molecular C-i symmetry determined from the structure of a crystal used for spectroscopy. The multiple progressions observed in the polarized spectra are rationalized in terms of the deviations from idealized D-4h point group symmetry and compared to the spectra observed for complexes with D-2h symmetry such as trans-[OsO2(oxalate)(2)](2-) that show only a single dominant progression for this transition.