We present results of the first photoreflectance (PR) study in Hg0.7Cd0.3Te and MBE and bulk Cd1−xZnxTe and the first detailed measurement of the variation of E1 optical transition energy with x in Cd1−xZnxTe at 77 K. Photoreflectance is a completely contactless form of electroreflectance. The E1 optical transition line shapes were measured and analyzed using currently available models. The MBE Cd1−xZnxTe samples exhibited E1 features that could not be fit satisfactorily, which may be due to the presence of an electron-hole interaction that was not included. The results indicate that the dependence of E1 with x may be expressed as follows: E1(x)=3.523 eV−0.022 eV ⋅ x+0.267 eV ⋅ x2. The linewidths of the E1 feature measured at 77 K in all the samples were much smaller than those at 300 K owing to the reduction in temperature broadening. This suggests that, in addition to being contactless, the characterization accuracy available with PR may be significantly better than that available in techniques such as electrolyte electroreflectance that are confined to room temperatures.