The metal-support interaction plays an important role in gold catalysis. We employ here crystalline cubic (α-) and hexagonal (β-) phases of heterometallic fluoride NaYF4 nanoparticles (NPs), obtained by the decomposition of a single source precursor [NaY(TFA)4(diglyme)] (TFA = trifluoroacetate), as nonoxide supports for gold catalysts. Using an isostructural gadolinium analogue, we also obtained doped α-NaYF4:Gd3+ and β-NaYF4:Gd3+ NPs. A successful deposition of ∼1% by weight gold NPs of average size 5-6.5 nm on these doped and undoped metal fluorides using HAuCl4·3H2O afforded Au/NaYF4 catalysts which were thoroughly characterized by using several physicochemical techniques such as X-ray diffraction, Brunauer-Emmett-Teller analysis, high-resolution transmission electron microscopy, energy-dispersive X-ray spectrometry, and X-ray photoelectron spectroscopy. A comparative study of the above catalysts for different oxidation reactions show that while for the aerobic oxidation of trans-stilbene in solution phase, they are either better (in terms of stilbene conversion) or at par (in terms of trans-stilbene oxide yield) in comparison to the reference catalyst Au/TiO2 of the World Gold Council, their activity toward CO oxidation reactions in gas phase remains much less than that of gold catalysts supported on metal oxides.