A highly efficient and chemoselective hydrogenation method was developed using a bimetallic PdFe catalyst. Pd and Ni catalysts failed in the tests performed. However, PdFe supported on carbon catalyst (10% w/w Pd and a molar ratio Fe/Pd=0.5) achieved interesting results. The selective nitro and aldehyde group reductions on the aromatic aglycone moiety were satisfactory. The desired products were obtained with high conversion and selectivity. A set of aryl O‐glycosides, such as bioactive Gastrodin, were prepared in very good yields and high β‐anomeric selectivity.