Solvent-resistant membranes are pivotal in industrial separations. This study aims to develop thin-film composite polyamide (TFC-PA) membranes with enhanced organic solvent nanofiltration (OSN) capabilities. Polyallylamine hydrochloride (PAAH) was used as the aqueous amine and isophthaloyl chloride (IPC) as the crosslinker to form the polyamide active layer by interfacial polymerization (IP) on a polyacrylonitrile (PAN) support. The impact of using anionic sodium dodecyl sulfate (SDS) and cationic cetyltrimethylammonium bromide (CTAB) to act as phase transfer agents during IP was investigated to understand their potential for facilitating the transfer of PAAH to the organic phase for reaction with IPC. The SDS and CTAB were separately dissolved into the PAAH solutions before IP to evaluate their effects on membrane properties. Extensive characterization including SEM, EDX, AFM, Water Contact Angle, ATR-FTIR, and Solid (CP-MAS) 13C NMR revealed various chemical and structural features of the membrane. The membrane M2 (PAAH-IPC) (exhibited >98% rejection for various anionic and cationic dyes. The inclusion of SDS during interfacial polymerization led to a substantial 3-fold increase in methanol permeate flux from 31 L m−2 h−1 to 119 L m−2 h−1, at a pressure of 15 bar. Conversely, the addition of CTAB resulted in membranes with higher permeate flux but insufficient dye rejection. Moreover, after three weeks of static aging of the membranes no significant changes were detected in either permeability or solute rejection, substantiating the stability of membranes.