Xyloglucan in water solution turns into a gel with addition of alcohol such as methanol and ethanol. In regard to this phenomenon, we investigated the adhesive property of alcohol to xyloglucan and proposed the mechanism of the gelation by molecular dynamics (MD) simulation of a xyloglucan in water, water/methanol, and water/ethanol solution for 10 ns. The alcohol molecules showed its adhesive property to the xyloglucan and made the swellingshrinking motion of the xyloglucan slow. Alcohol molecules solvated to the xyloglucan mainly in hydrophobic way so as to fill the void of water hydration shell, resulting in reformation of the hydrogen-bond network of water molecules around the solute. We also found that alcohol molecules have strong tendency to hydrogen-bond on xylose O3 in xyloglucan. According to these results, we proposed the gelation mechanism of xyloglucan in water/ alcohol solution.