[Re(CNx)5Cl] and Re(CNx)6 complexes form with the isocyanide ligand, 2,6-dimethylphenylisocyanide (CNx). [Re(CNx)5Cl] crystallizes in the space group P(2)1/c with a Re−Cl bond length of 2.5278(16) Å, a Re−C bond length trans to Cl of 1.937(6) Å, and Re−C bond lengths in the equatorial plane ranging from 1.998(6) to 2.034(6) Å. The complexes are highly emissive at 77 K with emission lifetimes of 5.1 and 4.6 μs, respectively, but are nonemissive at room temperature. Density functional theory (DFT) geometry optimizations of the ground and the triplet metal-ligand-to-ligand charge transfer (3MLLCT) states of the complexes in the gas phase place the energy of the 3MLLCT state for [Re(CNx)5Cl] 200 cm-1 higher than the experimental emission peak at 77 K. The energies of the singlet excited states of the two complexes calculated in ethanol using time-dependent density functional theory (TDDFT) and conductor-like polarizable continuum model (CPCM) deviate by less than 600 cm-1 from the corresponding UV−vis peaks in the same solvent. The TDDFT/CPCM calculation confirms the existence of 3d−d states that provide a nonradiative relaxation pathway accounting for loss of emission from the emitting state at room temperature. Calculations also reveal a singlet to triplet excitation at 35 700 cm-1 near the absorption of the CNx ligand at 35 200 cm-1 and a 3π→π* state of CNx 200 cm-1 higher than the experimental phosphorescence energy.