The ZnSe–ZnTe superlattices have attracted considerable attention as possible blue/green light emitters. Although these superlattices have been successfully fabricated and show intense photoluminescence, there are many basic issues about this system which still remain unresolved. The most important of them is the value of the valence band offset between ZnSe and ZnTe. We have studied the band structure of ZnSe–ZnTe superlattices. Our calculations are based on second orderk⋅ptheory and include the effects of strain and spin‐orbit splitting on the superlattice band structure. We have investigated the dependence of the superlattice band gap on the valence band offset. Based on the assumption that the photoluminescence from the superlattice corresponds to a bound exciton at a Te1isoelectronic center in ZnSe, we have fit the experimental photoluminescence data withk⋅ptheory to obtain the best value of the valence band offset. The value we find is 0.97±0.10 eV. Alternatively, assuming that the photoluminescence was due to band‐to‐band transitions we obtain a valence band offset of 1.20±0.13 eV. We have also calculated the superlattice band gap as a function of the constituent material layer thicknesses for the first valence band offset quoted. We expect these results to be important in gaining an understanding of the value of the valence band offset, and the nature of the photoluminescence from this system.