Present study focuses the effect of calcination temperature and its duration on the morphology and growth of nanograins in individual TiO2 nanofibers synthesized by electrospinning method. Polyvinyl acetate and titanium tetraisopropoxide were used as chemical precursors along with other standard solvents in the synthesis process. This study shows that synthesized TiO2 nanofibers are randomly arranged and spreads uniformly over the Si substrate and possess polycrystalline nature consisting of nanograins. Similar to the sintering behavior generally observed in bulk ceramics, the nanograins coalesce and grow under higher calcination temperature and longer calcination time. The activation energy for the growth of nanograins is found to be 47.2 kJ/mol. The dominant growth mechanism changes depending on the stages of calcination.