The discovery of facile methods to create complex lamellar structures in hydrogels, which mimic the exquisite structures in nature, remains a great challenge. In this work, an ordered lamellar structured hydrogel from the stimuli-responsive amino-polysaccharide chitosan is fabricated by an electro-assembly process, during which the diffusion of OH- and the electrophoresis of the chitosan chains play important roles. Importantly, a complex ordered/disordered structure of chitosan hydrogel can be regulated with high fidelity by programming the input electrical signals.