Vacuum annealing-based techniques for forming perovskite materials are provided. In one aspect, a method of forming a perovskite material is provided. The method includes the steps of: depositing a metal halide layer on a sample substrate; and vacuum annealing the metal halide layer and methylammonium halide under conditions sufficient to form methylammonium halide vapor which reacts with the metal halide layer and forms the perovskite material on the sample substrate. A perovskite-based photovoltaic device and method of formation thereof are also provided.