In the synthesis of the polyamide nanofiltration (NF) membrane, the hydrogen chloride is a by-product generated at the organic interface from interfacial polymerization, which reduces the reactivity of amine monomers due to protonation. Herein, a strategy of addition of an organic base in the organic phase to neutralize the H⁺ was reported. The performances of the membranes produced using three organic bases with different chain lengths were explored. The results showed that the organic base neutralized the H⁺ and promoted the rate of interfacial condensation reaction, which facilitated the formation of a dense and thin polyamide layer. Moreover, compared to control membrane, the membrane modified by organic base exhibited higher water permeance without sacrificing salt rejection. Higher diffusion rate of HCl through PES substrate compared to NF membrane indicated that HCl diffusion was mainly affected by the resistance of polyamide layer. Molecular simulations demonstrated that triethylamine (TEA) has lower energy barrier of neutralization and higher reaction heat in comparison with tripropylamine and N, N-diisopropylethylamine. The TEA modified membrane thereby displayed a permeance up to 24.3 L h⁻¹ m⁻² bar⁻¹ and Na₂SO₄ rejection of 98.8 %. This work provided a promising strategy for the regulation of interfacial polymerization in achieving high-permselective nanofiltration.