As expected, a thiol, an amine, and an alcohol could all be employed to obtain the corresponding thioester (29, 61% yield), amide (30, 74% yield), and ester (31, 61% yield) derivatives of dehydrocholic acid upon acyl substitution. Furthermore, we evaluated the possibility of forging C-C bonds. After a brief optimization of the reaction conditions already present in literature (see the SI for details), we were able to obtain ketone 32 in 46% yield by employing 1,3-dimethoxybenzene as the nucleophile, TMSOTf as additive, and ibuprofen as the acyl fluoride precursor in a Friedel-Crafts-type acylation reaction. In conclusion, we have developed a microfluidic reactor capable of safely producing SOF2, an overlooked reagent due to its gaseous and toxic nature, starting from the commodity chemicals SOCl2 and KF. This gas was generated in situ and reacted with a wide variety of carboxylic acids, including aromatic, aliphatic, and α-amino acid derivatives, to yield the corresponding acyl fluorides in a telescoped fashion. Furthermore, this method was capable of converting biorelevant molecules with perfect selectivity and in good chemical yields. Finally, as acyl fluorides are attractive intermediates for the synthesis of other acyl derivatives, we devised a streamlined three-module flow setup where, after the generation of the gas and the acyl fluoride production, the latter is directly reacted with a nucleophile to forge C-S, C-N, C-O, and C-C bonds. Based on these findings, we believe this flow approach makes thionyl fluoride a convenient reagent to convert carboxylic acids into acyl fluorides. Further applications of this strategy are ongoing in our laboratories.