Direct transformation of cellulose and sugarcane bagasse into 5-hydroxymethylfurfural (HMF) was carried out using single or combined metal chloride catalysts in DMA-LiCl solvent under microwave-assisted heating. Among several metal chloride catalysts studied, Zr(O)Cl-2/CrCl3 combined catalyst was most effective enabling 57% HMF from cellulose fiber. Zr(O)Cl-2/CrCl3 catalyst was also effective for the conversion of sugarcane bagasse to HMF and 5-ethoxymethyl-2-furfural (EMF), a promising biofuel. This report discloses one-pot synthesis of EMF from sugarcane bagasse for the first time and also reveals the maximum HMF yield known so far from sugarcane bagasse. Thus, the current catalytic system based on cheap and readily abundant zirconium and chromium salts presents an efficient method for EMF and HMF synthesis from inexpensive lignocellulosic biomass. (C) 2011 Elsevier Inc. All rights reserved.