Annealing multilayers of gadolinium hydroxide leads to the growth of gadolinium oxychloride crystallites film through a two-dimensionally confined process. The employment of a confined crystallization process creates a multi-layer film composed of mixed crystallites each doped with different activator ions, such as Eu3+ and Tb3+, which demonstrates a novel method of fabricating robust and semi-transparent inorganic thin films with multicolor emission capacity and color tunability.