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The association between electrospinning and polysaccharides corresponds to an important area under exploration, to meet the demands of biotechnological industries claiming for polymers with novel functional properties. Among the group of polysaccharides that attract attention for the manufacture of spun fibers; those from the marine origin that exhibit a remarkable potential, due to the possibilities to act as sulfated glycosaminoglycan mimics; as well as, exhibit an easily modifiable chemical structure that allow the production of derivatives suitable for biotechnological applications. Although electrospinning is a seemingly simple method, its applicability is not an easy task. The problem linked to the spinning of pure biomacromolecules has been generally evaluated embracing polymers from different origins. In this review, the parameters affecting the electrospinning of different marine polysaccharides in their pure form will be considered. The chemical features of these polysaccharides as well as the rheological aspects of their solutions will be in depth analyzed, emphasizing the difficulties associated with the use of water as the working solvent. Strategies used to produce spun fibers from other polymers will be also analyzed in this review, proposing them as an alternative to be studied when the production of spun fibers of marine polysaccharides is envisaged.