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Development of simple, low-cost and facile electrochemical sensor for DA detection is of great significance for the study and treatment of several neurological and psychiatric disorders. Herein, an innovative integration of honeycomb-patterned ordered porous structure with conductive reduced graphene oxide (rGO) was realized through the convenient breath figure method, in which the self-assembly of nontoxic and inexpensive water droplets were involved. Graphene oxide (GO) can be transferred to organic phase by surfactant via a simple self-assembly process to acquire the GO/surfactant complex, which was used as the casting solution in the breath figure method, and thus the skeleton of the porous structure. After electrochemical reduction, honeycomb-patterned porous rGO film was obtained. The prepared rGO-based porous structure modified electrode exhibited a high sensitivity of 1.18 μA/μM and low detection limit of 0.12 μM to DA detection, which are 2.5 and 0.07 folds to corresponding flat films, and are also comparable or even exceeding several functionalized graphene, GO or rGO composites sensor. In addition, excellent anti-interference, reproducibility, repeatability, long-term stability and good accuracy for DA detection in real samples were shown. Importantly, the porous structure can be easily adjusted by changing the preparation conditions, thereby regulating or optimizing the electrochemical sensing performance.