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We report on the structural, spectroscopic and radiative emission characteristics of Eu-doped BaTiO3 (BT) nanosystem as compared to the pure BT system. The structural analysis was performed by X-ray diffraction (XRD) studies where the nanoscale BT sample exhibits a perovskite structure with most intense peak along (1 1 0) plane that depicts the preferred crystallographic orientation. Also, the diffraction peak intensity was found to be suppressed for Eu-doped BT nanosystem. The nature of radiative emission was evaluated via steady-state photoluminescence spectroscopy (PL) and positron annihilation spectroscopy (PAS). The improved radiative emission response, with Eu2+ doping, was believed to be accompanied by 4f65d→4f7 transitions in case of Eu-doped BT system. Whereas, PAS lifetime study of doped sample has revealed longer lifetimes indicating thereby partial substitution of Ti4+ by Eu2+ in BaTiO3 system. [ABSTRACT FROM AUTHOR]