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In this work, we report the successful formation of MgO doped TiO2 nanocrystals (NCs) by simple wet-chemical method. The XRD exhibits a marginal decrease in the crystalline size of TiO2 nanosamples by the addition of MgO dopant. UV–Vis spectral analysis shows that the addition of MgO in TiO2 resulted in the red shift of the absorption edge. The optical energy band-gap and molecular vibrational analysis of doped nanosample was ascertained from photoluminescence (PL) and micro-Raman scattering technique respectively. HR-TEM analysis reveals that the substitution has sharply reduced the particle size of TiO2NCs.