Selected area electron diffraction pattern (SADP) and transmission electron microscopy (TEM) measurements were carried out to investigate the ordered structure in CdxZn1−xTe epitaxial layers grown on (001) GaAs substrates. The SADP showed to sets of superstructure reflections with symmetrical intensities, and the corresponding high-resolution TEM image showed a doublet periodicity in the contrast of the {111} lattice planes. The results of the SADP and the TEM measurements showed the existence of a CuPt-type ordered structured in the CdxZn1−xTe epitaxial layers. This CuPt-type ordered structure had two different variants with an antiphase boundary existing between the two variants. The formation of a CuPt-type ordered structure in a CdxZn1−xTe epitaxial layer might originate from the minimization of the strain relaxation energy in the reconstructed GaAs (001) surface. A possible atomic arrangement of and a formation mechanism for the CuPt-type ordered structure in the CdxZn1−xTe epitaxial layer are presented based on the TEM results. These results provide important information on the microstructural properties for improving the efficiencies of optoelectronic devices operating in blue-green spectral regions.