The cooperativity between red-shifted hydrogen bond and blue-shifting hydrogen bond in dimethyl sulfoxide aqueous solutions was studied by methods of quantum chemical calculations and infrared spectroscopy. The water molecule plays a different role in two types of hydrogen bonds: proton-donor in red-shifted hydrogen bond and proton-acceptor in blue-shifting hydrogen bond. The cooperativity is not prominent if the ring structure is formed through the OHcdots, three dots, centeredOS H-bond and CHcdots, three dots, centeredO(w) H-bond. However, if the methyl groups in the above ring structure participate in second CHcdots, three dots, centeredO(w) H-bond, the cooperativity is increased. The second CHcdots, three dots, centeredO(w) H-bond enhances OHcdots, three dots, centeredOS H-bond and weakens the first CHcdots, three dots, centeredO(w) H-bond.