We investigated the formation of index modulation for volume holograms consisting of poly-N-vinylcarbazole (PVCz), and achieved a new process that enables large holograms and uniform quality.Conventionally PVCz holograms are developed by two sequential dipping process: first into good solvent, then into poor solvent. When a swollen PVCz film is dipped into poor solvent, PVCz molecules precipitate into small grains. In the upper layer small grains can pack closely, because the solvent in the film can escape outside.However, the solvent in the lower layer is prevented from escaping by the closely packed upper layer, and the remaining solvent forms gaps corresponding to the degree of swelling. As the result of the difference in swelling between highly exposed and low exposed areas, refractive index modulation appears. Based on the investigation above, we found a new process where the holograms are developed by single dipping process into a mixture of volatile good solvent and nonvolatile poor solvent. When the film swollen by the mixture is carried out, the solvent in the film becomes poor solvent rich and small grains are formed. With this new process all areas of a hologram can be developed under same conditions, so large holograms with uniform quality becomes possible.