A series of Au(I) complexes containing unsymmetrical N‐heterocyclic carbene (imidazolylidene and benzimidazolylidene) functionalized with a xyloside group and an alkyl moiety (methyl and mesityl) was prepared using efficient procedures from D‐xylose. Their characterization was carried out in solution by multinuclear NMR, HR‐MS spectrometry and cyclic voltammetry, as well as in the solid state by means of single crystal X‐ray diffraction analysis for two of them. Evaluation of their ability to inhibit bacterial growth showed a preference for a Gram‐positive strain, Staphylococcus aureus, over a Gram‐negative strain, Pseudomonas aeruginosa.