Microcrystalline cellulose (MCC) is hydrolyzed to an appreciable extent (70 %) by using 1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate (IL-1) as effective catalyst. Valuable chemicals, such as 5-hydroxymethyl furfural (HMF) and furfural, are obtained in relatively high yields (15 % and 7 %, respectively). Interestingly, the introduction of FeCl2 as catalyst into IL-1 further enhances the catalytic activity, as proved by the higher conversion of MCC (84 %) and higher yields of HMF and furfural (34 % and 19 %, respectively) under the same experimental conditions, although small amounts of levulinic acid (LA) and total reducing sugars (TRS) were also found. The hydrolysis of MCC scarcely proceeded, or showed a lower efficiency, in the absence of catalyst (4 %) or with Al2O3 (7 %), inorganic acids (≤65 %), or several other ionic liquids (≤24 %) as catalyst. Dimers of furan compounds were detected as the main byproducts, as analyzed by HPLC–MS; from the mass spectrometry analysis, the components of the gas-phase products were determined to be methane, ethane, CO, CO2, and H2. A mechanism to explain the high activity of FeCl2 in the IL-1 system is proposed. Recycling of the IL-1 catalyst showed an almost constant activity during five successive trials. The simple and effective catalyst system may prove valuable in facilitating the energy-efficient and cost-effective conversion of biomass into biofuels and platform chemicals.