Herein, highly bendable air-working ionic polymer actuator was fabricated. Polyelectrolyte membrane in actuators was based on a nanostructured sulfonated styrenic pentablock copolymer (SSPB) and sulfonated graphene oxide (sGO) with large enhanced sulfonation degree as highly ion conduction-activating filler. The air-working actuator, achieved with introduction of ionic liquid (IL) in SSPB/sGO membrane, exhibited much larger actuation performance in the aspect of bending strain, initial strain rate, and charge-specific displacement. Moreover, ion transport behavior of IL in SSPB/sGO/IL actuator was investigated via tracking the movement of the IL's anion through energy-dispersive X-ray spectroscopy. In this observation, not only the mass transport of mobile ions but also the pumping effect with solvated ion complexes affect the deformation of SSPB/sGO/IL actuator.