We present the first experimental evidence for the breaking of the cubic symmetry in the band structure of CdZnTe epilayers deposited by metal-organic chemical vapor deposition (MOCVD). Polarized PL measurements along [110] and [(1) over bar 10] directions were performed and the valence band splitting (VBS) was determined. Growth conditions (growth temperature and partial pressure ratio) and type and misorientation of the substrates an correlated to the VBS of Cd1-xZnxTe epilayers.