Abstract The three-dimensional (3D) porous nanostructures have shown attractive promise for flexible microsupercapacitors due to their merits of more exposed electrochemical active sites, higher ion diffusion coefficient, and lower charge-transfer resistance. Herein, a highly opened 3D network of reduced graphene oxide/poly(3,4-ethylenedioxythiophene) (rGO/PEDOT) was constructed through the laser-assisted treatment and in situ vapor phase polymerization methods, which can be employed with gel electrolyte to prepare flexible microsupercapacitors, without conductive additives, polymer binder, separator, or complex processing. These porous open network structures endow the obtained microsupercapacitors with a maximum specific capacitance (35.12 F cm−3 at 80 mA cm−3), the corresponding energy density up to 4.876 mWh cm−3, remarkable cycling stability (with only about 9.8% loss after 4000 cycles), and excellent coulombic efficiency, which are comparable with most previous reported rGO-based microsupercapacitors. Additionally, the microsupercapacitors connected in series/parallel have been conveniently fabricated, followed by being integrated with solar cells as efficient energy harvesting and storage systems. Moreover, the working voltage or energy density of microsupercapacitors array can be easily tailored according to the practical requirements and this work provides a promising approach to prepare high-performance flexible micro-energy device applied in the wearable electronics accordingly.