Fibrous membranes are widely used in liquid-gas filtration and separation, porous structures formed by randomly cross-layered fibers have a significant influence on interfacial free energies, showing complex changes in contact angle. The present paper aims to measure the pore structures of a hydrophobic ((C2F4)n, PTFE) fibrous membrane by Confocal Laser Scanning Microscope (CLSM), and analyze the droplet contact angle hysteresis along its circumference. The capillary force of the solid-liquid interface is calculated by the surface integral of Laplace pressure on half droplet surface, and the solid-liquid and liquid-vapor interface area ratios are obtained according to the Cassie-Baxter model. The liquid penetration depth in pore structures is calculated by the quasi-equilibrium of the interface free energy. The experimental result shows that for the PTFE fibrous membrane, the liquid-vapor interface area ratio (f2The experimental result shows that for the PTFE fibrous membrane, the liquid-vapor interface area ratio (f2