Studies on the HCl-catalysed microwave-assisted dehydration of highly concentrated aqueous fructose (27 wt %) to 5-hydroxymethylfurfural (HMF) revealed a significant increase in the fructose conversion rate over the conventional heated systems. Water, being the most benign solvent and therefore ideal for green and sustainable chemistry, normally is a poor solvent for the dehydration process resulting in low HMF selectivities and yields. However, reaction at 200 °C with microwave irradiation with a short reaction time of only 1 s resulted in good HMF selectivity of 63% and fructose conversion of 52%, while prolonged irradiation for 60 s (or more) resulted in nearly full fructose conversion (95%) but lower HMF yield (53%). Decreasing the fructose concentration significantly improved the HMF selectivity, but possibly made the production route less attractive from an industrial point of view due to the resultant low throughput.