Hollow multilayered polyelectrolyte (PE) fibers were fabricated by the combination of the electrostatic layer-by-layer (LBL) and electrospinning methods. The influence of the deposition conditions on the structure of the obtained hollow multilayered PE fibers was studied systemically. The results showed that the formation of multilayered PE films on polystyrene (PS) fiber surface was strongly influenced by the number of repetitions of deposition and the pH value. The spaces among the adjacent fibers in fibrous mats were blocked by 15 poly(allylamine hydrochloride) (PAH)/poly(styrenesulfonate) (PSS) bilayers. The film growth speed was the highest in a strongly acidic solution. The theoretical Young's modulus of such a hollow multilayered PE nanofiber was also obtained to be around 21.6 GPa, which is much larger than that of normal synthetic organic fibers but is similar to that of human bone fibers. [DOI: