Polytetrafluoroethylene (PTFE) membranes are renowned for their excellent thermal stability, resistance to strong acids and alkalis, and superior mechanical stability. However, its inherent strong hydrophobicity significantly limits its use in water treatment. In this study, a SiO2 coating was successfully deposited in-situ on the surface of PTFE membranes using a hydrolyzed solution of tetraethyl orthosilicate (TEOS) compounded with the commercial fluorinated polyoxyethylene ether surfactant FS-31 (C6F13CH2CH2O(CH2CH2O)nH). The modification mechanism involves using the low surface energy nonionic fluorocarbon surfactant FS-31, which interacts hydrophobically with the PTFE substrate, serving as an “anchor” point around which the TEOS hydrolyzes and condenses around the fibers and nodes of the PTFE membrane, forming a complete and stable chemical network structure. The results show that the initial water contact angle of the modified membrane dropped to 36.5°, and the water flux reached 537.9 L m−2 h−1. After being continuously immersed in strong acid (5 wt% HCl), strong alkali (4 wt% NaOH), and oxidizing agent (5 wt% NaClO) for one week, the membrane maintained excellent hydrophilicity and stability. This study proposes a mild and efficient modification method to prepare durable hydrophilic PTFE membranes, portending great potential for applications in harsh environments.