Cobaltite of magnesium, embedded in polyvinylpyrrolidone (PVP) polymeric fibers forming nanocomposite were synthesized by combining conventional sol-gel method with electrospinning method. Ultrathin diameter polymer fibers containing nanoregime ceramic particles were obtained by varying various process parameters like voltage, concentration, feed rate, distance between nozzle tip and base plate on an indigenously assembled electrospinning unit. Polyvinylpyrrolidone (PVP) and polyvinylalcohol (PVA) polymeric fibers in nanoregime were also synthesized separately and the effect of the process parameters was observed on the fiber thickness and continuity. Characterization was done to verify the synthesis parameter effect on structural morphology of polymer based nanofiber composite. Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) were used as tools for study of structural morphology and its correlation with process parameters.