A facile approach to obtain electrode materials with excellent electrochemical properties is essential for the development of supercapacitors. We synthesized coral‐like Poly(3, 4‐ethylenedioxythiophene)/O−S‐doped porous carbon composites (PEDOT/S‐PCM) to be used as electrode materials for supercapacitors. S‐PCM was obtainted by the carbonization and activation of Poly(3, 4‐ethylenedioxythiophene)/reduced graphene oxide (PEDOT/rGO), and its structure was stabilized by doping the ablated Poly(3, 4‐ethylenedioxythiophene) (PEDOT) into the lamellae of graphene. The dual doping of sulfur and oxygen can prevent the graphene sheets from collapsing and provide an abundance of active sites. Under the optimized conditions, the PEDOT/S‐PCM composite shows a high specific capacitance of 278 F g−1 at a current density of 1 A g−1 and a significant capacitance retention of 91 % after 1000 cycles at a current density of 10 A g−1. PEDOT/S‐PCM could be a promising candidate as an electrode material for supercapacitor due to their good morphology and excellent electrochemical performance.