A comb copolymer with a fluorinated FPAE main chain and narrowly dispersed PMS graft chains has been prepared. The micellization behavior of this copolymer in a methanol/acetone mixture was studied. DLS studies showed hydrodynamic diameters of the micelles between 50 and 80 nm, while the diameters of dry micelles were ≈40 nm in TEM images. Micelle films with an interesting porous composite structure of nanofibers bearing micelle particles on the surface have been prepared by double coating the micelle solution. Superhydrophobicity with a WCA of 165° and a sliding angle of 3° was observed. As comb copolymers can adjust their molecular weight and block length independently, materials with a high physical strength and controllable morphological structure can be obtained.