Metal fluoroanions are of significant interest for fundamental structure and reactivity studies and for making isotope ratio measurements that are free from isobaric overlap. Iron fluoroanions [FeF(4)](-) and [FeF(3)](-) were generated by electrospray ionization of solutions of Fe(III) and Fe(II) with the fluorinating ionic liquid 1-ethyl-3-methylimidazolium fluorohydrogenate [EMIm](+)[F(HF)(2.3)](-). Solutions containing Fe(III) salts produce predominately uncomplexed [FeF(4)](-) in the negative ion spectrum, as do solutions containing salts of Fe(II). This behavior contrasts with that of solutions of FeCl(3) and FeCl(2) (without [EMIm](+)[F(HF)(2.3)](-)) that preserve the solution-phase oxidation state by producing the gas-phase halide complexes [FeCl(4)](-) and [FeCl(3)](-), respectively. Thus, the electrospray-[EMIm](+)[F(HF)(2.3)](-) process is oxidative with respect to Fe(II). The positive ion spectra of Fe with [EMIm](+)[F(HF)(2.3)](-) displays cluster ions having the general formula [EMIm](+) (n+1)[FeF(4)](-) n, and DFT calculations predict stable complexes, both of which substantiate the conclusion that [FeF(4)](-) is present in solution stabilized by the imidazolium cation. The negative ion ESI mass spectrum of the Fe-ionic liquid solution has a very low background in the region of the [FeF(4)](-) complex, and isotope ratios measured for both [FeF(4)](-) and adventitious [SiF(5)](-) produced values in close agreement with theoretical values; this suggests that very wide isotope ratio measurements should be attainable with good accuracy and precision when the ion formation scheme is implemented on a dedicated isotope ratio mass spectrometer.