Different metal halide catalysts supported on a commercial active charcoal have been synthesized, activated, characterized and tested in glucose dehydration to 5-hydroxymethylfurfural using a biphasic water/methyl isobutyl ketone media. The influence of the cation nature (K⁺, Ca²⁺, Sr²⁺, Mg²⁺) and anion nature (F^–, Cl^–, Br^–) on the catalytic performance of the solid is discussed in terms of glucose conversion, HMF yield and products selectivity. The activation of the impregnated catalysts results in a great diversity of active sites, such as Bronsted sites (carboxylic groups), basic sites (metal oxide), and Lewis acid site (Mⁿ⁺). Their distribution within the samples determinates the resulting products and the final HMF yield.