An extremely high rate of holographic surface relief grating inscription has been achieved in materials based on a solid state ring-opening reaction of an oxirane with amino substituted azobenzenes. A number of effective formulations based on various oxirane derivatives and different aminoazobenzene derivatives has been prepared. For one of the best formulations, a low molecular weight three-armed azobenzene derivative has been separated in a pure form. This three-armed azobenzene derivative exhibited the highest inscription rate.