Cadmium telluride (CdTe) epitaxial films (EFs) were grown on near-lattice-matched Cd0.96Zn0.04Te (CZT) substrates by molecular beam epitaxy at different ambients to achieve Cd-rich samples with extra Cd molecular flux or Te-rich samples with extra Te molecular flux. The evolution of epitaxial growth was in situ monitored by reflection high-energy electron diffraction (RHEED). A two-dimensional growth mode was indicated by the streaky RHEED patterns. Crystal structures of the CdTe EFs were characterised by X-ray diffraction (XRD). XRD data suggested that the crystal quality of the CdTe EFs was improved by controlling the Cd and Te flux ratio. Low-temperature photoluminescence (PL) spectra were carried out in these CdTe EFs. The typical characteristic peak at similar to 1.552 eV denoted as the bound-to-free transition was only found in CdTe samples grown under an extra Cd flux, and Cd vacancy-related defects were absent in the Cd-rich EFs, confirming the Cd-rich or Te-rich states of the epitaxial CdTe films. Finally, minority carrier lifetime was prolonged in Cd-rich CdTe EFs as supported by time-resolved photoluminescence (TRPL) measurement. (C) 2016 Elsevier B.V. All rights reserved.