Using metalorganic vapor‐phase epitaxy, zinc selenide films are grown on GaAs surfaces of three different orientations: (100), (100) tilted 2° off toward ⟨011⟩, and (100) tilted 5° off toward ⟨011⟩. The properties of these epilayers are determined by x‐ray diffraction and photoluminescence. There is remarkable difference in lattice relaxation mechanism between exact (100) case and 5° off, a part of lattice mismatch stress in the ZnSe layer on 5° off substrate is relaxed by lattice inclination. This inclination prevents the generation of defects and dislocations. Photoluminescence properties are also improved by using the tilted substrates. Strong near‐band‐edge emission and weak deep‐level emissions such asY0,S, andSAlines compared with those grown on exact (100) substrates are observed.