The cyclopentadienyl complex Cp*Ir(PMe3)Cl2 reacts with the dipotassium salt of phthalic acid in the presence of AgPF6 via chloride substitution to give the ortho-metalated compound Cp*Ir(PMe3)[C6H3(CO2)(CO2H)]. This new compound has been isolated by recrystallization and has been characterized in solution by 1H and 13C NMR spectroscopies, and the solid-state structure has been verified by X-ray crystallography. Cp*Ir(PMe3)[C6H3(CO2)(CO2H)] crystallizes in the monoclinic space group P21/c, a = 9.1010(6) Å, b = 16.715(1) Å, c = 14.3965(9) Å, β = 108.24(1)°, V = 2080.0(2) Å3, Z = 4, and d calc = 1.813 mg/m3; R = 0.0276, R w = 0.0810 for 2730 reflections with I > 2σ(I). Coordination of the benzene ring to the iridium center via one of the carboxylate groups and ortho-metalation of the C–H moiety that was α to the iridium-bound carboxylate group is confirmed.