HgCdTe epilayers grown by chemical vapor deposition (MOCVD) on GaAs substrates operating in the long-wave infrared range were characterized by the photoluminescence (PL) method. Photodiode and photoconductor designs, both (100) and (111)B crystallographic, were analyzed. Spectral current responsivity (RI) and a PL signal approximated by a theoretical expression being the product of the density of states and the Fermi–Dirac distribution were used to determine the fundamental transition (energy gap, Eg). For all the samples, an additional deep-level-related transition associated with mercury vacancies (VHg) were observed. The energy distance of about 80 meV above the valence band edge was observed for all the samples. Moreover, measurements at low temperature showed shallow acceptor-level (AsTe and VHg as acceptors) transitions. In HgCdTe(100), due to the higher arsenic activation, AsTe was the dominant acceptor dopant, while, in HgCdTe(111)B, the main acceptor level was formed by the neutral VHg. The determined activation energies for AsTe and VHg dopants were of about 5 meV and 10 meV, respectively.