The asymmetric unit of (P)-chloridobis[(S)-(+)-5-(3,5-dioxa-4-phosphacyclohepta[2,1-a:3,4-a']dinaphthalen-4-yl)dibenz[b,f]azepine]iridium(I)-benzene-pentane (1/1/1), [IrCl(C34H22NO2P)2]·C6H6·C5H12, contains two formula units. The two symmetry-independent molecules of the Ir complex have similar conformations and approximate C2 symmetry, with small deviations arising from slightly different puckering of the seven-membered dioxaphosphacycloheptadiene rings. The Ir atoms have trigonal-bipyramidal coordination geometry, with the P atoms in axial positions. The steric strain of the bidentate coordination of the P-alkene ligand through its P and alkene C atoms causes the N atom to have pyramidal geometry, compared with the trigonal-planar geometry observed in the free ligand. The coordination also results in an anti conformation of the binaphthyl and alkene groups within the P-alkene ligand.