The structure determination of (eta4-1,5-cycloocta-diene)(pyridine)[tris(2,4,6-trimethoxyphenyl)phos-phine]iridium(I) hexafluorophosphate, [Ir(C27H33-O9P)(C8H12)(C5H5N)][PF6] revealed approximate square-pyramidal geometry at the Ir atom with one of the methoxy groups of the phosphine ligand being weakly bound in the apical position [Ir...O = 2.857 (4) angstrom].