Oxidation of hydroxyarenes is one of the strategies towards the synthesis of structural moieties found in naturally occurring quinones. Quinones are known to possess a broad spectrum of biological activities. Bi-promoted Au catalysts, supported on silica, were synthesized using deposition (DP) and microwave-assisted loading (MW) methods. The prepared catalysts were systematically characterized for their physicochemical properties by X-ray diffraction (XRD), nitrogen physisorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The morphology of the catalyst is dependent on the catalyst synthesis method used. For Au–Bi catalysts prepared by MW, Bi is present as octagonal BiOCl plates with a tetragonal crystallographic structure, while catalysts prepared by DP show Bi being present as folded sheets. Their catalytic activities and selectivities were tested through the oxidation of 2,3,5-trimethylhydroquinone (TMHQ) and 4-methoxy-1-naphthol (MNL), in which 2,3,5-trimethyl-1,4-benzoquinone (TMBQ) was produced from TMHQ while 4,4-dimethoxy-2,2′-binaphthalenyl-1,1′-diol (BNL), and 4,4′-dimethoxy-2,2′-binaphthalenylidene-1,1′-dione (BNP) were obtained from MNL. Catalytic data obtained for the oxidation of TMHQ demonstrated that the activities and selectivities obtained in these reactions depend on the structure of the catalyst, solvent and temperature used. Up to 100% TMHQ conversion with 78.2% TMBQ yield were achieved, while 71.5% conversion of MNL with 54.9% BNP yield were obtained. The effect of solvents on the catalytic outcomes of the oxidation of TMHQ was conducted at r.t using MW-5Au5Bi catalyst in MeOH and MeNO2. Under these conditions, no conversion of TMHQ was observed in MeOH, while 56.9% conversion of TMHQ was achieved in MeNO2 under the same reaction conditions. Generally, both MW and DP-synthesized catalysts showed low to moderate activities in the oxidative transformation of TMHQ, with the exception reactions on MW-5Au5Bi in MeOH. Similar to TMHQ, the catalytic outcomes in the reaction of MNL highly depend on the temperature and structure of the catalyst. For example, 10.1 and 71.5% conversions of MNL were achieved at r.t and 60 °C, respectively, over DP-5Au5Bi catalyst in MeOH. The catalyst exhibiting “folded sheets” morphology showed better activity compared to the catalyst with a “packed sheets” morphology. For example, up to 71.9% conversion was achieved on DP-5Au5Bi (“folded sheets” morphology), while only up to 39.3% was achieved on DP-1Au1Bi (“packed sheets” morphology).