The development of thin-film composite membranes has gained more importance as they exhibit higher permeability, higher solute rejection and improved antifouling behavior. The incorporation of hydrophilic nanomaterials within the composite thin film has reported to effectively increase the hydrophilicity and improve the membrane performance. In this study novel thin-film composite nanofiltration membranes were prepared by interfacial polymerization of trimesoyl chloride, polyvinylpyrolidone (PVP) and montmorillonite (MMT) composite on the porous polyethersulfone membrane. The effect of preparation parameters was studied as; reaction time, PVP concentration and MMT content. The properties of the prepared composite thin-film membranes were analyzed in terms of their chemical structure, surface morphological features, pure water contact angle, zeta potential, pure water permeation flux (PWP) and solutes rejection. The prepared composite thin-film membranes showed smoother surfaces, different surfaces functionality and amphoteric surfaces with points of zero charge at pH 7–7.5. The PWP was found to increase with increasing MMT content up to 0.10 wt%. The rejection of crystal violet dye (CV) was studied using the prepared membranes. The membrane with 0.5% PVP, 0.10% MMT and 6 min reaction time showed PWP of 18.1 L/m2 h bar and CV rejection of 80.01%. The rejection of Na2SO4 and MgCl2 increased with increasing MMT content and reached 96% and 35.4%, respectively. The steady state flux was decreased by 5% with increasing MMT content from 0.10 to 0.12 wt% indicating improved antifouling behavior with MMT.