While polysaccharide graft copolymers and glycopolymers have been widely studied and used in various applications, linear block copolymer structures combining a polysaccharide segment and a synthetic one have been less described. The limited availability of the polysaccharide reducing‐end, the difficulty of finding a common solvent of both blocks and the need sometimes to protect the lateral hydroxyl groups of the polysaccharide chain may explain the relatively low number of studies on this copolymer family despite its potential interest. Polysaccharide block copolymers feature physicochemical properties not only close to those of synthetic block copolymers but also bring an added value such as the biodegradability, the biocompatibility or the bioactivity in some cases. This review aims at presenting the synthetic pathways towards such structures, from the basic polymerization techniques to the most recent ones including controlled/living polymerization mechanisms and also by emphasizing the chemical reactions used to functionalize the reducing‐end of the polysaccharide block. The amphiphilic nature of most of the polysaccharide‐based block copolymers reported so far gives rise to various self‐assembly morphologies in the solid state or in selective solvents. In addition, the rigidity of the polysaccharide block is expected to influence the microphase separation of the block copolymer by increasing the thermodynamic incompatibility between dissimilar blocks. A special interest was drawn to the formation and the properties of polymer vesicles (polymersomes) in aqueous solutions. Polysaccharide block copolymers might represent a new class of biomaterials with potential applications in different fields such as the plastic industry, the detergency and also the pharmaceutics where the design of nanodevices carrying a native polysaccharide chain is of interest for therapy, vaccination and diagnosis purposes.
