The photophysical processes in a series of isocyano Re(I) phenanthroline complexes {[Re(CNR)n(CO)4‐n(phen)](PF6); n=2, 3, 4, R=2,6‐(iPr)2C6H3‐ or tBu‐ (n=2)} in acetonitrile have been studied by resonance Raman spectroscopy, transient resonance Raman spectroscopy, and femtosecond / nanosecond transient spectroscopy to elucidate the nature of their electronic transitions and emissive excited state(s). The kinetics of the intersystem crossing, vibrational relaxation and radiative decay of the metal‐to‐ligand charge transfer {MLCT [dπ(Re)→π*(phen)]} excited state have also been determined.