This work reports the catalytic conversion of corn starch into 5-hydroxymethylfurfural (HMF) in the presence of AlCl3 center dot 6H(2)O in water-[Bmim]Cl/MIBK biphasic media. Among the varieties of corn starch investigated (regular, waxy, and native high amylose), a maximum of 64 wt % HMF was obtained from waxy corn substrates within 20 min of reaction time at 140 degrees C. The HMF yield was comparable to the yield obtained from fructose and glucose which were of 70 and 68 wt % respectively. Furthermore, MIBK effectively partitioned HMF from the aqueous to the organic phase, thereby preventing further HMF rehydration to levulinic acid (LA). Thus, negligible LA yields (0.1 wt %) were detected in this system. Additionally, [Bmim]Cl and AlCl3 center dot 6H(2)O can be recycled for several catalytic runs without compromising the HMF selectivity. In summary, the proposed process parameters are favorable to achieve high HMF yields from amylopectin-rich starches.