Crystals of Ph(3)PAuX and Ph(3)AsAuX where Ph = phenyl and X = Cl and Br exhibit dual phosphorescences from two excited states. The higher energy system achieves a maximum relative intensity at low temperatures. Its origin is at approximate to 360 nm in all of the complexes, and it is assigned to an intraligand phosphorescence from a phenyl localized (3) pi pi* state. The zero-field-splitting parameters of the state are D approximate to 0.2 and E approximate to 0.04 cm(-1). The lower energy system has its origin at approximate to 460 nm in all of the complexes and tentative splitting parameters of D approximate to 0.09 and E approximate to 0.005 cm(-1). The phosphorescence rates of the individual spin levels at 1.4 K range from approximate to 5 x 10(3) to approximate to 10 s(-1), with the higher energy system having the larger rates. SCF-X alpha-SW calculations on H3PAuCl, H(2)PhPAuCl, Ph(3)PAuCl, PhPH(3)(+), and PhH are also reported for comparison with the experimental results.