Polytetrafluoroethylene (PTFE) capillary membranes, known for the great chemical resistance and thermal stability, are commonly used in membrane separation technologies. However, the strong hydrophobic property of PTFE limits its application in water filtration. This study introduces a method whereby acrylamide (AM), N, N-methylene bisacrylamide (MBA), and vinyltriethoxysilane (VTES) undergo free radical copolymerization, followed by the hydrolysis-condensation of silane bonds, resulting in the formation of hydrophilic three-dimensional networks physically intertwined with the PTFE capillary membranes. The modified PTFE capillary membranes prepared through this method exhibit excellent hydrophilic properties, whose water contact angles are decreased by 24.3–61.2%, and increasing pure water flux from 0 to 1732.7–2666.0 L/m²·h. The enhancement in hydrophilicity of the modified PTFE capillary membranes is attributed to the introduction of hydrophilic groups such as amide bonds and siloxane bonds, along with an increase in surface roughness. Moreover, the modified PTFE capillary membranes exhibit chemical resistance, maintaining the hydrophilicity even after immersion in strong acidic (3 wt% HCl), alkaline (3 wt% NaOH), and oxidative (3 wt% NaClO) solutions for 2 weeks. In conclusion, this promising method yields modified PTFE capillary membranes with great hydrophilicity and chemical resistance, presenting substantial potential for applications in the field of water filtration.