Photoluminescence (PL) spectra of epitaxial (100) and (111) CdTe on (100) GaAs and (211), (331), and dual epitaxy, (211) and (331) CdTe on (211) GaAs substrates, prepared by low-pressure metal-organic chemical vapour deposition, are presented. Steady-state PL measurements were carried out at temperatures ranging from 11.4 K to 200 K. The well-known 1.47 eV band was observed for all samples. PL bands at 1.36 and 1.32 eV, which were reported only once before for CdTe films were grown on (111) CdTe substrates, were observed for the dual epitaxy sample. These features are probably caused by the radiative recombination of electrons and holes trapped at a localised centre associated with a less-common structural defect.