In this study, 3D network architectures are constructed using nano-sized graphene oxide (nGO) as the building block. The cross-linking reaction of nGO is conducted in sub-micrometer water droplets in an emulsion system to control the size of the networks by restricting the reaction space. Two types of 3D GO networks having different cross-linking lengths were constructed, and their methyl orange adsorption and release behaviours were investigated under external stimuli, such as thermal treatment, ultrasonic wave treatment, and near-infrared light irradiation.