LAUSR

An ultrafine‐fibrous polytetrafluoroethylene (PTFE)–SiO2 membrane was successfully fabricated using the solution blow spinning (SBS) method. This membrane demonstrated superhydrophobicity (water contact angle > 150°) and oleophilicity (ethyl acetate contact angle = 0°) compared to a commercial PTFE membrane. Additionally, the SBS PTFE–SiO2 membrane exhibited a high porosity of 83% compared to 55% in the commercial PTFE membrane. When used for membrane‐assisted extraction, the PTFE–SiO2 membrane exhibited a higher caffeine transport rate (3.84 × 10−7 m s−1) than the commercial PTFE membrane (2.18 × 10−7 m s−1). The addition of SiO2 nanoparticles provided better hydrophobicity and higher phase stability during membrane‐assisted solvent extraction. Given the excellent thermal and chemical stability of PTFE–SiO2, this type of membrane shows potential for high‐value solvent extraction and stable long‐term operation with no emulsion generation. The SBS method offers a promising alternative for the sustainable fabrication of PTFE membranes on a larger scale without the need for organic solvents or lubricants.