The CdGa2Se4 layers were grown by the hot-wall epitaxy method. From the absorption measurement, the band-gap variation in CdGa2Se4 was well interpreted using Varshni’s equation. After the postannealing in various ambient, the behavior of point defects in CdGa2Se4 was investigated by measuring photoluminescence (PL). Point defects originating from VCd, VSe, Cdint, and/or Seint were classified as donor or acceptor types. Thus, the Ga in CdGa2Se4 did not form native defects because the Ga existed in the form of stable bonds in CdGa2Se4. Based on these PL results, we schemed out a band diagram of the recombination process in CdGa2Se4.