The combination of high-voltage windows and bending stability remains a challenge for supercapacitors. Here, we present an “advantage-complementary strategy” using sodium lignosulfonate as a pseudocapacitive molecule to regulate the spatial stacking pattern of graphene oxide and the interfacial architectures of graphene oxide and polyaniline. Flexible and sustainable sodium lignosulfonate-based electrodes are successfully developed, showing perfect bending stability and high electronic conductivity and specific capacitance (521 F·g⁻¹ at 0.5 A·g^–1). Due to the resulting rational interfacial structure and stable ion-electron transport, the asymmetric supercapacitors provide a wide voltage window reaching 1.7 V, outstanding bending stability and high energy-power density of 83.87 Wh·kg^–1 at 3.4 kW·kg^–1. These properties are superior to other reported cases of asymmetric energy enrichment. The synergistic strategy of sodium lignosulfonate on graphene oxide and polyaniline is undoubtedly beneficial to advance the process for the construction of green flexible supercapacitors with remarkably wide voltage windows and excellent bending stability.