In this work, we have investigated the relationship between photoluminescence and structural evolution of BaTiO3 nanocrystals. Their structure, and phase transformation correlation with their growth behaviors are investigated using X-ray diffraction, advanced electron microscopy, and Raman spectroscopy. The correspondence photoluminescence of BaTiO3 nanocrystals shows different intensity at the different growth stages. Through detailed microstructural characterizations and analysis, we have found that BaTiO3 nanocrystals processed the structural transformation from disorder to order and a crystal size increase with the reaction going on, which maybe lead to an enhancement in the tetragonal phase. Such disorder structure and the polarization effect of the tetragonal phase were the dominant factors for improving the PL, which will be tailored during the different growth stages. (C) 2015 Elsevier B.V. All rights reserved.