The hydrogen bond and aggregation structures of polyvinyl alcohol (PVA) gels prepared with dimethylsulfoxide (DMSO) were investigated as were the the rheological properties. The variable temperature Fourier Transform Infrared (FTIR) and X-ray results of PVA-DMSO gels show that the hydrogen bond and crystalline structure are destroyed as temperature increases. In the Tanaka model, the value of ζ (the number of sequential units per chain in the junction) is 1.45 and s (the number of polymer chains in a single junction), which reveals the ability of solution to form gel, varied as a function of gel melting temperature T gm . The results of dynamic rheology show that the elastic modulus G′ is proportional to the gel concentration and inversely proportional to the temperature. It was found that gels formed from solutions with same viscosities showed different properties. This is because a gel with a higher polymerization degree has a lower value of s.