A new type of superlattice in consisting of a periodic sequence of ultrathin p‐ and n‐doped layers (also called “nipi” crystal) has been achieved by molecular beam epitaxy (MBE). The individual p‐ and n‐type layers of which the structure is composed were doped with beryllium as acceptor and silicon as donor impurities, respectively. Low temperature photoluminescence studies and transport measurements were performed first to attest a superior quality of the intentionally p‐ and n‐doped constituent layers and of the characteristics of the individual p‐n junctions prepared by MBE. The existence of a novel superlattice effect in the periodic p‐n doping multilayer structures in was then established by studying the optical absorption tails which extend far into the gap of the unmodulated semiconductor depending on the constituent doping levels and on the artificially introduced periodicity of the crystal.