Silica and vanadium doped silica nanoparticles were obtained by sol–gel technique using ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethane sulfonate, [EMIM][TfO]. In order to understand characteristics of the nanoparticles without IL, we synthesized silica and vanadium doped silica nanoparticles without IL. Synthesis was also conduced without IL to interpret the nanoparticles characteristics in absence of IL. As-synthesized, as well as calcined (400°C/4h) nanoparticles were evaluated by HR-SEM, XRD, FTIR and TGA characterization. Morphology and size of the nanoparticles were found to be influenced due to the presence of IL during the synthesis. The EDX showed 8–10wt% presence of vanadium on silica surface validating the formation of vanadium doped silica nanoparticles. Photodegradation efficiency of doped nanoparticles were assessed for methylene blue. Among different nanoparticles synthesized, vanadium doped and IL assisted silica nanoparticles showed higher photodegradation due to the reduced band gap energy substantiated by measurement of bandgap by UV-DRS.