Vesicles are often used for intercellular communication in biology, like in the nervous system. In such systems, intact vesicles can be restrained (or mobilized) by association with (or release from) a cytoskeletal scaffold. We mimic the restraint of vesicles in vitro using a biopolymer network – chitosan - by two different approaches. First, we tethered vesicles to a chitosan scaffold based on the interaction between the hydrophobes of modified chitosan and vesicles. The network shows pH-responsive behavior and can be cleaved enzymatically since chitosan is an aminopolysaccharide and biodegradable. Second, vesicles and liposomes can be restrained in the electrodeposited chitosan films by co-deposition with chitosan. The restraint can be spatiotemporally controlled in response to electrical signals. Intact vesicles can be mobilized from the film under mildly acidic conditions. Potentially, both approaches will provide convenient and controllable means to store, liberate and deliver vesicle-based reagents/therapeutics for microfludic/medical applications.