In this study, we report the emissive properties of a heteroleptic cyclometalated Ir(iii) complex, [Ir(bzq)2(PBO)] (bzqH = benzo[h]quinoline; PBOH = 2-(2-hydroxyphenyl)benzoxazole). The complex, [Ir(C^N)2(N^O)], was synthesised and optically resolved using a chiral column. Two geometrical isomers,trans-(N,N) andcis-(N,N) isomers, were obtained as the major and minor products in an enantiopure form, respectively. Their molecular structures were determined using single crystal X-ray analysis. In the crystalline states, the intermolecular C-H⋯π interaction between PBO−and an H atom in bzq−was the main factor influencing molecular packing. When the complexes were dissolved in CH2Cl2and excited at 430 nm under N2atmosphere, yellow (λmax= 550 nm) and orange emissions (λmax= 570 nm) were observed for thetrans-(N,N) andcis-(N,N) isomers, respectively, with the quantum yield higher for the former than the latter.