Petroleum-independent and economically viable production of 5-hydroxymethyl-2-furfural (HMF) from industrially supplied high fructose corn syrup (HFCS) using a wood powder-derived carbonaceous solid acid in an ethylene glycol (EG)-based solvent was developed. EG-based solvents were preferable to the dehydration of HFCS into HMF owing to stabilizing reversible intermediates. In addition, low boiling EG-based solvents were readily removed to isolate HMF. As a parametric study on the dehydration of HFCS into HMF in an EG-based solvent, effects of reaction temperature, initial concentration of fructose, catalyst dosage, and water content on reaction rate and HMF yield were investigated. Sulfonated amorphous carbonaceous materials (similar to 0.7 mmol of SO3H/g) were prepared from wood powder via incomplete hydrothermal carbonization and then sulfonization, and they were applied to the dehydration of HFCS in glyme, affording HMF in 80% yield. It was also found that a prolonged reaction enabled further conversion of HMF into levulinic acid in a highly selective manner.