It was used the Complex Polymerization Method to synthesize barium calcium titanate powders (BCT). Crystalline Ba(0.8)Ca(0.2)TiO(3) perovskite-type phase could be identified by X-ray diffraction and confirmed by Raman spectroscopy in the powders heat treated at 600 degrees C. Inherent defects, linked to structural disorder, facilitate the photoluminescence emission. The photoluminescent emission peak maximum was around of 533 nm (2.33 eV) for the Ba(0.8)Ca(0.2)TiO(3). The photoluminescence process and the band emission energy photon showed dependence of both the structural order-disorder and the thermal treatment history. The results revealed that Ba(0.8)Ca(0.2)TiO(3) (BCT20) is a highly promising candidate material for optical applications. (C) 2009 Elsevier B.V. All rights reserved.