According to the Freeman theory, increasing the backbone stiffness to some extent is an effective way to obtain the remarkable membrane with both high permeability and selectivity. In this work, a high performance nanofiltration (NF) membrane was prepared via tailoring the polyester/polyamide backbone stiffness. The flexible monomer-piperazine (PIP) and the rigid monomer-bisphenol F (BPF) were selected as the aqueous phase monomers, and they were interfacial reacted with trimesoyl chloride (TMC) on the polyethersulfone (PES) UF membrane to generate the polyester/polyamide layer. By mixing PIP with BPF, both of the polyester/polyamide backbone stiffness and microporosity degree enhanced. As a result, the PIP/BPF NF membrane possessed a 2.6-fold pure water flux (PWF) of the PIP NF membrane (the salt rejection remained at the same level), and 4.8-fold PWF of the BPF NF membrane. Our results revealed a novel and facile way to improve the NF membrane performance.