We present the results of the first ab initio molecular dynamics simulations, based on the Car-Parrinello method, of glucose in water, performed to investigate structural aspects of the anomeric equilibrium in aqueous solution. The analysis of the hydrogen bonds around the crucial anomeric oxygen shows a distinct solvation behavior for the beta and alpha anomers. While the beta anomer, which is the most abundant in water, allows the water molecules to flow in a disorderly manner around its anomeric site, the alpha anomer tends to bind them more tightly.