Thermo-responsive chitosan hydrogel system (TRCHS) was prepared and its microstructure was investigated by scaning electron microscope (SEM) and mercury intrusion poremaster (MIP). Based on analyzing the data, a special porosity property was reported at the first time. Its gelling mechanism was studied by a group of contrast experiments. Results may provide experimental and theoretical supports for how to apply it on tissue engineering scaffold and how to influence or control its essential properties.