Porous structures have been attracting the attention of scientific researchers in the field of oil cleanup. Herein, highly porous poly (vinylidene fluoride) (PVDF) fiber webs with a novel spindle porous bowl like beads, as well as spindle porous beads, were electrospun successfully. The surface morphology and porous structures of as-prepared PVDF webs were characterized. Moreover, the wettability properties of electrospun webs were demonstrated. Furthermore, the results showed that the spindle porous bowl like beads webs have an outstanding oil absorption capacity, which exhibitions a bright future for oil-water separation. We believe that such spindle porous bowl like beads of the electrospun PVDF fiber webs will extend the variety of their applications in the field of oil cleanup, self-cleaning materials, and so on.