Nanofiltration (NF) has become a widely used technology in water treatment due to its environmental friendliness, energy efficiency, cost-effectiveness, and operational simplicity. However, polyamide (PA) NF membranes still face challenges, including low permeate flux, limited resistance to organic pollutants, and inadequate resilience to residual chlorine. To address these issues, this study developed a thin-film composite (TFC) NF membrane featuring a separation layer of sandwich structure. Initially, a single separation layer of polyvinyl alcohol (PVA) NF membrane was prepared, followed by the fabrication of a PA layer on its surface, and ultimately, a second PVA layer was constructed on the PA layer. The experimental results show that the PVA/PA/PVA sandwich structure TFC exhibits high permeability to pure water and robust resistance to both pollution and residual chlorine. The PVA-0.20/PA/PVA-0.20 TFC, prepared with a 0.20%w/v PVA solution, achieved a pure water flux of up to 22.05 L m−2 h−1 bar−1 (LMH/bar), which was 2.92 times higher than that of the control TFC membrane. Additionally, it demonstrated a salt rejection rate exceeding 96% for Na2SO4 and over 99% for Congo Red (CR) and Victoria Blue B (VB). In comparison with the control TFC membrane, the PVA-0.20/PA/PVA-0.20 membrane exhibited significantly enhanced resistance to pollution. Following immersion in a 1000 ppm NaClO solution for 4 h, the rejection rate of the control TFC membrane decreased markedly and that of the PVA-0.20/PA/PVA-0.20 membrane decreased marginally, indicating excellent resistance to residual chlorine. Due to the robust overall performance of the PVA/PA/PVA membrane, it holds potential advantages for application in treating reclaimed water or slightly polluted water.