AbstractA new class of biodegradable anionic surfactants with structures based on 5‐alkoxymethylfuroate was prepared starting from 5‐hydroxymethylfurfural (HMF), through a one‐pot–two‐steps process which involves the selective etherification of HMF with fatty alcohols using heterogeneous solid acid, followed by a highly selective oxidation of the formyl group with a gold catalyst. The etherification step was optimized using aluminosilicates as acid catalysts with different pore topologies (H‐Beta, HY, Mordenite, ZSM‐5, ITQ‐2, and MCM‐41), different active sites (Bronsted or Lewis) and different adsorption properties. It was shown that highly hydrophobic defect‐free H‐Beta zeolites with Si/Al ratios higher than 25 are excellent acid catalysts to perform the selective etherification of HMF with fatty alcohols, avoiding the competitive self‐etherification of HMF. Moreover, the 5‐alkoxymethylfurfural derivatives obtained can be selectively oxidized to the corresponding furoic salts in excellent yield using Au/CeO2 as catalyst and air as oxidant, at moderated temperatures. Both H‐Beta zeolite and Au/CeO2 could be reused several times without loss of activity.