III/V semiconductors containing dilute amounts of N exhibit remarkable features such as a strong increase of the effective mass of the electrons, a huge red‐shift of the band gap compared to the host material and a weak pressure dependence of the PL band position. We examined these features by studying the affect of N incorporation onto the band formation of the alloys Ga(NAs) and Ga(NP). The dispersion‐free N‐related impurity band interacts in a repulsive way with the conduction band of the host material. The novel As‐rich Ga(NAsP) alloy exhibits both the electronic as well as the mechanical properties to serve as an active laser material for III/V integration onto Si substrates. We studied the optical properties by means of photoluminescence, excitation and modulation spectroscopy as well as pressure dependence. Energies of the interband transitions within the MQW have been successfully simulated by a type I QW calculation, yielding a CB to VB offset ration of about 1:2. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)