This study focuses on developing a novel polysulfone (PSF) dense hybrid membrane modified with nonionic surfactants, Tween 20 (T20) and Triton X-100 (X100), for improved pervaporation (PV) dehydration of bioethanol. The modified membranes were then examined for their ethanol dehydration performance, microscopy and spectroscopy characteristics, surface charge, mechanical and roughness properties, crystallinity structure, differential scanning calorimetry (DSC), swelling, and contact angle (CA) analysis. The free volume structure of the membranes was assessed using positron annihilation lifetime spectroscopy (PALS) and Doppler broadening spectroscopy (DBS). A significant discovery from this analysis was the semi antiplasticizing effect observed when surfactants were added to the PV membranes. The PV results revealed that incorporating 0.5 wt% T20 into PSF significantly improved the total flux and PSI of PSF/T20 to 226.35 g/m2 h and 46578 g/m2 h, respectively. Similarly, the total flux and PSI of hybrid membranes containing X100 increased to 110.19 g/m2 h and 43680 g/m2 h. Consequently, the developed PSF/T20 membranes demonstrated more significant potential for bioethanol dehydration compared to PSF/X100 membranes.