The surface morphology of nanomaterials has been attracting the attention of researchers in order to determine their advantages-related properties. In this work, polyvinylidene fluoride (PVDF) branched nanofibers are directly electrospun with a diameter of less than 35 nm at low relative humidity. The surface morphology and branched structure of as-prepared PVDF webs are characterized. Furthermore, the wettability properties of electrospun fiber webs are demonstrated. The results show that PVDF branched nanofibers have tiny diameters, excellent water contact angle, outstanding specific surface area, and high oil absorption capacity, which exhibit a bright future in the field of oil absorption. We believe this study can be served as a good reference for the preparation, characterization, and application of the branched structure for oil-water separation.