Crystals of {(Me(2)PhP)AuX}(n) (Me = methyl; Ph = phenyl; X = Cl, Br, I; n = 2, 3) show emission from two excited states. Both states are assigned a triplet multiplicity, on the basis of their lifetimes and zero-field splittings. The structured, higher energy emission originates at approximate to 360 nm and has the greater relative intensity at low temperatures. It is assigned as intraligand phosphorescence from a phenyl-localized (3) pi pi* state. The unstructured, lower energy emission has a peak wavelength that varies in the range 630-730 nm. It is assigned as phosphorescence from the triplet state due to the gold-based sigma(p) <-- sigma*(s,d) excitation. The corresponding singlet state is observed at 290-310 nm. The results of SCF-X alpha-SW calculations on the model complexes H(3)PAuX and (H(3)PAuX)(2) are also presented.