In this work is described an innovative synthesis route for hydrophobic ionic liquids (ILs) composed of N-methyl-N-alkylpyrrolidinium (or piperidinium) or imidazolium or tetralkylammonium cations and (perfluoroalkylsulfonyl)imide, ((C n F2n+1SO2)(C m F2m+1SO2)N−), anions. This synthesis does not require the use of any environmental unfriendly solvent such as acetone, acetonitrile or halogen-containing compounds, which is not welcome in industrial applications. Only water is used as the process solvent throughout the entire process. In addition, the commonly used iodine-containing reagents were replaced by the cheaper, more chemically stable and less toxic bromine-containing compounds. A particular care was devoted to the development of the purification route, which is especially important for ILs to be used in high-energy electrochemical devices such as high voltage supercapacitors and lithium batteries. The effect of the reaction temperature, the time and the stoichiometry in the various steps of the synthesis have been investigated in detail. This novel procedure allowed obtaining ultrapure (>99.9wt.%), clear, colourless, inodorous ILs with an overall yield above 92wt.% and moisture content below 1ppm. NMR measurements were run to confirm the chemical structure whereas elemental analysis and electrochemical tests were performed to check the purity of the synthesized ILs.