In this work, we are reporting on effect of calcination time on structural, optical absorption, and radiative emission features of solid-state derived BaTiO3 nanoscale systems calcined at 1000 oC and hence suggesting an optimum calcination time for effective fabrication. In the work, the electron microscopic imaging study depicts homogeneously distributed pseudo-cubic nanoparticle of typical dimension ~7-10 nm, whereas the XRD patterns suggests that the samples are in ferroelectric tetragonal phase with preferred orientation along (110) crystal plane. It was also noticed that the degree of preferred orientation of the crystallites increases with increase in heat treatment time. Increase in crystallite size with temperature was another important feature. However, dislocation density and micro-strain was found to be minimum in case of the sample calcined for moderate time only (4 hour). The absence of a sharp endothermic peak in DSC curves is attributed to size inhomogeneity and varying polycrystallinity in the specimens. From the analysis of UV-visible absorption spectra, the optical band gap of BaTiO3 was found to be maximum in the 4-hour heat treated sample. The broad luminescence response of nano-BaTiO3 system is discussed in the light of quantum confinement effect, near band-edge features, defects states, and self-trapped excitons. It was also observed that the calcination time hugely influences the limit of contributions of different contributors to the emission response.