A kind of bioinspired heterostructured bead-on-string fiber (BHBF), composed of poly-(methyl methacrylate) (PMMA) and titanium tetrachloride (TiCl4) hydrolyzed nanoparticles, was prepared via integrating a wet-assembly system, including PMMA electrospinning, fog of nanoparticles and water coalescence at multi-stages. The wet-assembly of BHBF was regulated by the difference in surface energy and Laplace pressure. Especially, BHBF is characteristic of a hydrophilic rough bead for excellent water collection ability.