Thin-film composite (TFC) nanofiltration membranes are prepared via interfacial polymerization with a polyphenol coating as an interlayer for the thin and smooth polyamide selective layer. The polyphenol interlayer is simply fabricated by the codeposition of tannic acid and diethylenetriamine without changing the surface morphology of the polysulfone ultrafiltration substrate. An interfacial polymerization is conducted from piperazidine and trimesoyl chloride on the polyphenol interlayer to construct the polyamide selective layer. The as-prepared TFC nanofiltration membranes show nearly tripled fold of water permeation flux as compared with those prepared at the same condition without an interlayer. They also exhibit a high rejection to Na2SO4 (>98%) because the thin and defect-free polyamide selective layer is formed on the polyphenol interlayer. These nanofiltration properties have high reproducibility, which means the TFC nanofiltration membranes are suitable for scale-up industrial applications.