In this article, we describe the synthesis of new and ion-selective nanofiltration (NF) membranes using polyvinylidene fluoride (PVDF) nanofibers and hyperbranched polyethylenimine (PEI) as building blocks. These new nanofibrous composite (NFC) membranes consist of crosslinked hyperbranched PEI networks supported by PVDF nanofibrous scaffolds that are electrospun onto commercial PVDF microfiltration (MF) membranes. A major objective of our study was to fabricate positively charged NF membranes that can be operated at low pressure with high water flux and improved rejection for monovalent cations. To achieve this, we investigated the effects of crosslinker chemistry on membrane properties (morphology, composition, hydrophobicity, and zeta potential) and membrane performance (salt rejection and permeate flux) in aqueous solutions (2,000 mg/L) of four salts (NaCl, MgCl2, Na2SO4, and MgSO4) at pH 4, 6, and 8. We found that an NFC-PVDF membrane with a network of PEI macromolecules crosslinked with trimesoyl chloride has a high water flux (similar to 30 L m(-2) h(-1)) and high rejections for MgCl2 (similar to 88 %) and NaCl (similar to 65%) at pH 6 using a pressure of 7 bar. The overall results of our study suggest that PVDF nanofibers and hyperbranched PEI are promising building blocks for the fabrication of high performance NF membranes for water purification.