Composite optical thin-film materials have received a significant amount of interest in order to relieve the material constraints on refractive indices as well as reducing the number of layers required in optical coating design. Amongst others binary zirconia-silica composite thin films have attracted considerable attentions due to their several favorable opto-mechanical properties. In the present studies such a composite system under certain compositional mixings displayed both refractive index and band gap supremacy over pure zirconia films violating the most popular Moss rule. This unexpected evolution has several practical applications one of which can be directly employed in extending the range of tunability of the refractive index. Besides, the probing of such a novel evolution through the analysis of ellipsometric refractive index modeling and morphological correlation functions has revealed several novel as well as superior microstructural properties in the composite thin film systems. All these characterization and analysis techniques distinctly indicate a strong interrelation between the microstructural ordering and superior optical properties of the present zirconia-silica codeposited composites. (c) 2006 Elsevier B.V. All rights reserved.