An efficient, mild and rapid synthesis of α‐fluoroketones has been developed, via a fruitful association between gold and Selectfluor starting from aldehyde‐yne and alkynylaryl ketone derivatives. Several functionalized and synthetically highly valuable α‐fluoroketones (21 compounds, up to 92%) were isolated in good to excellent yields via a remarkable regioselective oxyfluorination reaction in EtOH/H2O at room temperature. We have shed some light on parts of the mechanism by reacting diphenylacetylene and aldehyde‐yne with or without Selectfluor. The reaction most presumably occurs via a sequential gold‐catalyzed regioselective hydration followed by the α‐fluorination reaction, but the presence of aldehyde moiety is crucial for the reactivity of alkyne function. The fluoroketones were efficiently transformed to 4‐fluoroisoquinolines (9 compounds, 82–95%) of high pharmaceutical interest.