<p>This study focuses on the development of tetraethylorthosilicate (TEOS) crosslinked poly(vinyl alcohol) (PVA) membranes incorporating bentonite (BNT), montmorillonite (MMT), and zeolite-A (ZEO-A). The physicochemical properties of the resulting membranes were analysed using techniques such as FT-IR, WXRD, TGA and DSC. Before subjecting the membranes to pervaporation studies, sorption studies were conducted in various water-isopropanol compositions. The influence of different nanofillers on pervaporation performance was systematically investigated for water-isopropanol mixture separation at varying temperatures. Among the membranes, the ZEO-A incorporated membrane exhibited the highest separation factor of 382, with a flux of 6.459 × 10⁻² kg m⁻² h⁻¹ for 10 mass% water in the feed. The total flux and the water flux overlapped, suggesting effective breaking of the water/isopropanol azeotropic point. The activation energy for water permeation (<i>E</i>_<i>pw</i>) was significantly lower than that of isopropanol (<i>Ep</i>_<i>IPA</i>), indicating superior separation ability of the ZEO-A incorporated PVA-TEOS membrane, particularly in isopropanol dehydration. Moreover, the negative heat of sorption (<i>∆H</i>_<i>s</i>) for all membranes suggested dominance of Langmuir’s sorption mode.</p> Graphical abstract <p></p>