ZnS0.1Se0.9/ZnSe strained layer superlattices with up to 120 periods were grown by metalorganic vapor phase epitaxy. We demonstrate the sensitivity of room temperature photoluminescence of these structures for the assessment of the dependence of structural properties on growth conditions. Low temperature photoluminescence (PL) and x‐ray diffraction data confirm the results of the room temperature PL measurements. In optimized samples showing highly efficient blue luminescence (2.71 eV) at 300 K heavy‐hole and light‐hole free exciton recombinations at 11 K and higher‐order satellite reflections in the x‐ray diffraction profiles were observed.