The synthesis of [NMe₄][AuF₄] and [NEt₄][AuF₄], as well as an improved one‐pot synthesis of Cs[AuF₄], is reported. The new [AuF₄]⁻ salts were structurally characterized by single crystal X‐ray diffraction, NMR spectroscopy, vibrational spectroscopy, and mass spectrometry. These salts are the first gold(III) fluoride salts that can be isolated in pure form and are convenient to be used in usual organic solvents for subsequent synthesis. The formation of molecular AuF₃ complexes in solution is further reported, characterized as [F₃Au(NCCH₃)] at low temperature, as [F₃Au(py)] and a binuclear derivative which are stable at room temperature. The stability of these species in common organic solvents was investigated and they showed a satisfying stability.