Herein novel mesoporous silica film nanocomposites are successfully synthesized by using phosphorescent columnar assembly of an amphiphilic trinuclear gold (I) pyrazolate complex [Au3Pz3] as a functional template in the sol-gel synthesis. By controlling the molar ratios of silica source tetrabutylorthosilicate (TBOS) to [Au3Pz3] in an acidic aqueous alcohol solution from 60:1 to 20:1, highly ordered phosphorescent nanocomposites can be fabricated with hexagonal [Au3Pz3]/silicahexand lamellar [Au3Pz3]/silicalamsilicates.