Metallic bismuth and Bi-oxyfluoride nanoparticles (NPs) are successfully synthesized by non-reactive and reactive sputtering of a Bi target onto 1-butyl-3-methylimidazolium bis(trifluoro-methylsulfonyl)imide ([BMIM][TFSI]) ionic liquid (IL). Non-reactive sputtering is realized in pure Ar plasma, where isotropic, well crystallized and dispersed Bi NPs of 3-7 nm are obtained. The diameter and the size distribution of these NPs do not significantly vary with the power, gas pressure, and sputtering time; but these sputtering parameters seem to influence the NPs concentration. Then, the introduction of O2 and CF4 gases in addition to Ar enables the reaction of radicals from plasma with Bi clusters at the liquid top surface to form Bi-oxyfluoride NPs of 3-12 nm in diameter with a photocatalytic activity. Hence, the reactive sputtering onto an IL is an efficient, original and promising method for synthesizing Bi-based compound NPs. Finally, we propose a mechanism based on reactions of species from plasma at the IL surface to explain the formation of Bi-compounds by reactive sputtering.