Superhydrophobic fiber films, as a typical superhydrophobic material, have advantages such as self-cleaning, non-wettability, and pollution resistance. They can be widely used in oil-water separation, antibacterial, anti-pollution, anti-icing, and self-cleaning fields. Traditional electrospun superhydrophobic fiber films face difficulties in fabricating fibers with large contact angles due to the non-Newtonian fluid flow and Taylor cone jet trajectory limitations. To address this challenge, this study develops a novel ultrasonic-magnetic field coupling electrospinning strategy for fabricating poly(methyl methacrylate)-polystyrene (PMMA-PS) fibrous films with enhanced superhydrophobicity. Physical, chemical, and contact angle measurements were used to analyze the morphology, composition, and hydrophobic properties of the fabricated films. The results showed that by controlling the blend ratio of PMMA and PS and optimizing the electrospinning process with ultrasonic vibration and magnetic field coupling, PMMA-PS fibers with better fiber refinement, closer spindle-shaped arrangements, and significantly increased roughness were successfully fabricated. When using 15% PMMA and 15% PS solutions, the static contact angle of the resulting fiber films reached 173.1°, demonstrating the best superhydrophobicity. The study suggests that optimizing the surface morphology of the nanofibers is an effective method to improve hydrophobicity and provides a new approach for fabricating superhydrophobic fiber films.