The design of smart hydrogel actuators fully constructed from natural polymers for assessing the biomedical applications is important but challenging. Herein, an extremely simple, green, and ultrafast strategy is presented for preparing robust gradient all-polysaccharide polyelectrolyte complex hydrogel actuators. Driven by diffusing of low molecular weight chitosan into high molecular weight sodium alginate solution, a nanoporous, ultrastrong, and gradient chitosan/sodium alginate complex hydrogel film with adjustable thickness can be directly generated on the interface of two solutions within minutes. The as-prepared film can provide superfast temperature, ionic strength, and pH-triggered programmable deformations, and perform a distinct sequential double folding behavior due to the competitive effect between complexed and noncomplexed segments of polyelectrolyte. Besides, patterning Ca 2+ to locally crosslink sodium alginate in the film enables various more complex shape transformations. This green and simple diffusion-driven strategy provides significant guidance for fabricating bio-friendly actuators with applications in drug delivery, tissue engineering, soft robotics, and active implants. drug delivery, [6] tissue engineering, [7] biomimetic actuators, [8] medical devices, [9] etc. [10] The 3D deformation of self-shaping hydrogel actuator stems from their preprogrammed heterogeneous structures, [11] which cause the in-plane and/or out-ofplane mismatches in volume change upon the trigger of external stimuli. [12] Despite the considerable progress that has been made recently in terms of the sophistication of the shapes and the diversity of the function for self-shaping hydrogels, [13] their applications in biomedicine and engineering remain challenging. The major limitations include the unsatisfactory biocompatibility and biodegradation of synthetic polymers involved in existing hydrogel actuators, as well as their poor mechanical properties and long characteristic response time. [14] Currently, there is a growing demand for developing a broadly applicable method toward designing the ultrastrong hydrogel actuators composed entirely of natural polymers to assess the practical applications.Natural polyelectrolytes are the ideal candidate materials for the hydrogel actuators. Besides inherently prominent advantages of renewability, biocompatibility, and biodegradability for nature polymers, [15] they possess the ability of changing their own conformations in response to external stimuli (e.g., pH and IS). [16] To integrate polyelectrolytes into macroscopic materials, layer-by-layer (LBL) assembly is the most commonly used fabrication method, which is carried out by sequential adsorption of oppositely charge polyelectrolytes onto various substrates. [17] However, the time-consuming LBL technique can only generate ultrathin films on a nanometer scale that cannot be used as freestanding material unless by chemical posttreatment, and thus is inapplicable for the fabricating of biocompatible hydrogel actuators. [...