The photophysics of the series of tungsten and molybdenum arylcarbyne complexes Cp(CO){P(OMe)(3)}M=C-Ar (1a, M = W, Ar = phenyl; 1b, M = Mo, Ar = phenyl; 1c, M = W, Ar = o-tolyl; 1d, M = W, Ar = 2-naphthyl) has been examined by using absorption, emission, and transient absorption spectroscopy. Extended Huckel calculations indicate that the lowest excited state of these arylcarbyne complexes is based on a d(M) --> pi* - (M=C-Ar) configuration. Consistent with this prediction, each of the complexes displays a weak, mid-visible absorption band which is attributed to the d --> pi* transition. The tungsten complexes la, Ic, and Id also exhibit red luminescence with a lifetime in the 100-200 ns regime. Nanosecond laser flash photolysis studies indicate that the arylcarbyne complexes display a strong transient absorption with a maximum in the 400-450 nm region. Close correspondence between decay lifetimes obtained by luminescence and transient absorption indicate that the transient absorption may be assigned to the d --> pi* excited state.