The photofunctionality of the cobalt-hexacarbene complex [Co(III)(PhB(MeIm)(3))(2)](+) (PhB(MeIm)(3) = tris(3-methylimidazolin-2-ylidene)(phenyl)borate) has been investigated by time-resolved optical spectroscopy. The complex displays a weak (Phi similar to 10(-4)) but remarkably long-lived (tau similar to 1 mu s) orange photoluminescence at 690 nm in solution at room temperature following excitation with wavelengths shorter than 350 nm. The strongly red-shifted emission is assigned from the spectroscopic evidence and quantum chemical calculations as a rare case of luminescence from a metal-centered state in a 3d(6) complex. Singlet oxygen quenching supports the assignment of the emitting state as a triplet metal-centered state and underlines its capability of driving excitation energy transfer processes.