Solvation behaviors of N-isopropylacrylamide (NIPAM) in water/methanol mixtures are investigated by molecular dynamics simulations. The results indicate that NIPAM solvent interactions are weakened with the increase of methanol mole fractions (x(methanol)) from 0.25 to 0.80, rationalizing the reentrant coil-to-globule-to-coil transition behaviors of poly(N-isopropylacrylamide) in the mixed solvents. Interestingly, hydrogenbonded water/methanol clusters are abundant in binary mixed solvents, leading to the decrement of NIPAM solvent interactions. To better understand the intermolecular interactions in the water/methanol complex clusters, the structures of pure water and methanol clusters are also studied for a comparison. Although the amount of water clusters decreases with an increase in x(methanol), the structure of water clusters stays stable, and hydrogen-bonded networks are not essentially disrupted. As for methanol molecules, they prefer to form short nonbranched chainlike hydrogen-bonded clusters. However, most of the chainlike hydrogen-bonded methanol clusters are broken in water-rich solutions, leaving the little probability for the formation of dimeric and trimeric methanol clusters.