Defects in Silicalite-1 (structure type MFI) generate acid sites in the form of (i) hydroxyl nests present inside the channels or (ii) Bronsted-Lewis acid pairs, associated with terrace step kink sites present on the external surface of zeolite crystals. The amount of the sites has been changed by controlling the thermal treatment and pH value during preparation, or by post-synthesis treatments (ionic-exchange, silylation). These sites have been quantified by NMR, XRD and FT-IR pyridine adsorption/desorption at room temperature and 150 degrees C, and correlated with the catalytic etherification of 5-hydroxymethyl-2-furfural (HMF) with ethanol, a relevant reaction to produce diesel additives. The results show that the surface acidity of Silicalite-1 materials presents an heterogeneous distribution of Lewis and Bronsted acid sites with different degrees of strength. The amount and distribution of such active centers determine the catalytic performance in HMF etherification. It is also shown that adsorption of water, produced in situ by ethanol condensation, has a promoter effect at lower concentration and high temperature, due to the dissociation of S2R siloxanes bonds, and formation of Lewis and Bronsted acid centers with medium-high strength, responsible for the activation pathways of HMF conversion to 5-(ethoxymethyl)furfan-2-carbal dehyde (EMF) and ethyl-4-oxopentanoate (EOP), respectively. (C) 2015 Elsevier Inc. All rights reserved.