Composite hydrogels based on hydroxypropyl cellulose (HPC) and graphene oxide (GO) were developed and used for adsorption of phenol. The single network composite hydrogel (SNCH) was first prepared by crosslinking of HPC and GO by epichlorohydrin; then the SNCH was treated with polyethyleneimine solution, forming the double network composite hydrogel (DNCH). The DNCH exhibited better adsorption capacity than the SNCH due to larger surface area and more functional groups. The possible adsorption mechanism of the composite hydrogels toward phenol involved electrostatic, hydrogen bonding, and π–π interactions. Study on dynamic adsorption behavior of phenol by SNCH and DNCH indicated that the breakthrough time increased when the initial concentration and feed flow rate of phenol decreased. Furthermore, the breakthrough time of DNCH was longer than that of SNCH at all operating conditions due to the relatively higher adsorption capacity of DNCH. The SNCH and DNCH could be repeatedly used without significant loss in the initial binding affinity after six adsorption–desorption cycles, which indicated that the composite hydrogels were qualified for practical application.