Tailoring the surface morphology of fibers has been attracting unlimited attention in various areas. In this work, branched polyvinylidene fluoride (PVDF) nanofibers are directly electrospun with a diameter of less than 40 nm using a tetrabutylammonium chloride (TBAC) at the relative humidity (RH) of 10%. The formation mechanism of the branched structure is demonstrated. The mechanical properties, crystalline phases, and piezoelectric properties of the branched nanofibers are investigated. The results show that the branched PVDF nanofibers have excellent mechanical properties, high crystallinity, supreme beta-phase content (F[beta]), as well as outstanding electrical outputs. We believe this work can be used as a good reference for the preparation, characterization, and application of the branched structure for energy harvesting.