Here, we report on the effect of chemical substitution on the structural and optical properties of Cu-doped CaTiO3 (CTO) polycrystalline powders synthesized by the polymeric precursor method. Our findings are discussed based on the structural order-disorder effects originating from the modification of the Ca1-xCuxTiO3 microcrystal matrix. These results may elucidate the compositional modulation and methods of controlling the structural design, as well as reveal the changes in the optical behavior of this system at an atomic level. (C) 2016 Elsevier Ltd. All rights reserved.