There are challenges in developing practically viable biopolymer-based actuators with ecofriendly, biocompatible, and biodegradable functionalities. Therefore, we propose a cellulose acetate (CA)-based ecofriendly soft-ionic networking actuator consisting of multifunctional additive polyvinylidene difluoride (PVDF), highly conductive ammonia-functionalized graphene nanoplatelets (AFGNPs), ionic liquids (IL), and flexible conducting polymer poly(3,4-ethylenedioxuthiopene)-polystyrene sulfonate (PEDOT:PSS) as an electrode. The proposed actuator exhibits a large bending displacement and short response time in an open-air environment, resulting from its enhanced electro-chemo-mechanical properties and strong ionic and interfacial interactions. In comparison with CA/PVDF-IL actuator, the CA/PVDF–IL–AFGNPs actuator demonstrates a considerably increased IL uptake and ion-exchange capacity of up to 71.04% and 300.6%, respectively, and an increase in the specific capacitance by over 3.64 times, which lead to bending actuation performances 2.21 and 1.87 times greater, respectively, under AC (4 V) and DC (4 V). Moreover, we demonstrate that a CA/PVDF–IL–AFGNPs actuator with a hierarchical structure shows values that are 1.32, 1.5, and 1.74 times larger than those of a planar actuator in DC (4 V), AC (3 V), and blocking force (4 V), respectively. The developed high-performance CA/PVDF–AFGNPs and the hierarchical surface texture of the patterned CA/PVDF–IL–AFGNPs actuators present these extraordinary achievements together with environmentally friendly materials, a low driving voltage, easy manufacturing, and high actuation performances. Therefore, they can be candidates for human-friendly products (e.g., biomedical devices, bioinspired robots, and soft haptic devices).