<p>A magnetic field assisted wire electrical discharge machining and electrochemical machining process (MF assisted WEDM-ECM) is proposed to fabricate two-tiered microstructures on the surface of thick nickel-titanium (NiTi) alloys. The objective is to significantly improve processing quality and efficiency, thereby enhancing surface hydrophobic properties for orthopedic implant applications. Firstly, a simulation model for continuous pulse discharge craters is developed by incorporating a Gaussian heat source and heat transfer theory. By coupling the deflection effect of the magnetic field on electrons with electrode dynamics, a model was established for the time-varying electric field and current in the electrolytic processing region under the influence of a magnetic field. Subsequently, this model was combined with a continuous pulse discharge model to establish a simulation model for the formation process of two-tiered microstructures under MF assisted WEDM-ECM. Secondly, a contact angle prediction model is developed to analyze surface hydrophobicity, combining Wenzel and Cassie-Baxter’s theories. The simulation results indicate that surface roughness decreases and contact angle increases with wider pulse widths and higher peak currents, resulting in enhanced hydrophobicity. Finally, a Taguchi orthogonal experimental design is employed in MF assisted WEDM-ECM. The results demonstrate significant improvements: a 41.97% reduction in recast layer thickness, a 16.06% decrease in surface roughness, and a 10.67% increase in average contact angle. The minimal errors (8.54% and 9.98%) between simulated, predicted, and experimental contact angles verify the theoretical framework’s reliability.</p>