The electrospinnability of FucoPol, a bacterial exopolysaccharide, is presented for the first time, evaluated alone and in combination with other polymers, such as polyethylene oxide (PEO) and pullulan. The obtained fibers were characterized in terms of their morphological, structural and thermal properties. Pure FucoPol fibers could not be obtained due to FucoPol’s low water solubility and a lack of molecular entanglements. Nanofibers were obtained via blending with PEO and pullulan. FucoPol:PEO (1:3 w/w) showed fibers with well-defined cylindrical structure, since the higher molecular weight of PEO helps the continuity of the erupted jet towards the collector, forming stable fibers. WAXS, DSC and TGA showed that FucoPol is an amorphous biopolymer, stable until 220 °C, whereas FucoPol-PEO fibers were stable until 140 °C, and FucoPol:pullulan fibers were stable until 130 °C. Interestingly, blended components influenced one another in intermolecular order, since new peaks associated to intermolecular hierarchical assemblies were seen by WAXS. These results make FucoPol-based systems viable candidates for production of nanofibers for packaging, agriculture, biomedicine, pharmacy and cosmetic applications.