Research on superhydrophobic surfaces received continued attention due to more and more widely applications of superhydrophobic materials. Two parameters have been recognized for the rational design of the superhydrophobic materials: surface texture and chemical constitution. In this work, we fabricated composite membranes of polystyrene-block-poly (ethylene-co-butylene)-block-polystyrene (SEBS) and fluorinated polyhedral oligomeric silsesquioxane-block-polystyrene (FPOSS-PS) using a sequential electrospinning and electrospraying approach. Composite membranes with hierarchical geometries could be achieved by adjusting the formulation and/or fabrication protocols. Incorporation of fluorinated component enhances the surface property of the composite membranes due to its ultra-low surface energy, while micron particles attached on the surface further promotes the robustness of the membrane and enhanced the cell/tissue anti-adhesion efficiency. With a simple annealing treatment, the physical crosslinking was built up between the micron particles and underlying fibers, rendering the membranes with good stability and anti-adhesion properties. These superhydrophobic membranes are anticipated to have potential applications in wound-dressing and other related areas.