Vanadium pentoxide (V2O5) nanoparticles were synthesized at moderate reaction temperatures by hydrolysis of VO[OCH(CH3)(2)](3) in two different air- and water-stable ionic liquids with the same anion: 1-butyl-1-methyl pyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py-1,Py-4]Tf2N) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIM]Tf2N) via the sol-gel method using acetone and isopropanol either as refluxing solvents or as co-solvents. The cation type of the ionic liquid affects the crystallinity, morphology, and surface area of the produced nanoparticles: [Py-1,Py-4]Tf2N gave products with higher crystallinity especially with acetone as a refluxing and co-solvent, while [EMIM]Tf2N gave a clear mesoporous morphology with isopropanol as a refluxing solvent. Ionic liquids affect the key factors (morphology and surface area) that make V2O5 an attractive material as catalyst and/or cathodic material for lithium ion batteries.