The electronic properties of (ZnSe)n/(Si2)m (111) superlattices (SLs) are investigated theoretically in order to clarify the general features of the zone-folding and the band-mixing effects in superlattices composed of an indirect-band-gap semiconductor (Si). The detailed electronic structure of (ZnSe)n/(Si2)m (111) SLs are studied with the range n = m = 10–16, giving special attention to the role of the interface states at the Zn–Si and Se–Si polar interfaces. The presence of the electric field in the SL is totally ignored, i.e., “the zero-field model.” The degeneracy of the energy minima of the conduction band at the M point in the zinc-blende-type bulk material cannot be lifted by the zone-folding effects alone. The band-mixing effect through the interfaces between the two constituent materials plays an important role in determining the overall band lineup throughout the entire Brillouin zone. The states at the conduction- and valence-band edges are confined two dimensionally in the Si layers. Furthermore, we have found two interface bands in the lower and upper regions of the gap. The states of the lower interface band are located at the Zn–Si interface, while those of the upper interface band are located at the Se–Si interface. The energies of the interface states depend on the parameters representing the Zn–Si and Se–Si bond lengths and the valence-band discontinuity between ZnSe and Si, but the interface states do not disappear from the gap with reasonable choices of the parameters. The electronic structure of the superlattice turns out to be quite sensitive to the combination of the well and barrier layer thicknesses. This sensitivity suggests the possibility of designing suitable band structures for device applications. Furthermore, the absorption spectra of the superlattices are calculated and are found to be quite different from those of bulk ZnSe and Si but fairly close to their average. The electronic and optical properties suggest that superlattices composed of indirect-band-gap semiconductors offer great potential for application to optical devices.