Titanium alloys with special macro-micro composite structures of directional hydrophobicity are difficult to prepare due to poor thermal conductivity and good corrosion resistance, inhibiting the wide engineering applications for aerospace, marine engineering, and biomedicine. To prepare macro-micro composite structures on the surface of titanium alloys and achieve directional hydrophobicity, the sub-millimeter structures with an edge width of 150 μm, a groove width of 250 μm, and a depth of 250 μm were fabricated on the titanium alloy by wire electrical discharge machining (WEDM) technology, and high voltage-induced weak electric arc machining (HV-μEAM) was used to fabricate micro-scale feature size micro-structures on the processed macro-structure edges. The influence of process parameters on the morphology of microstructures was studied experimentally. The smooth surface of the titanium alloy is isotropically hydrophilic, and its contact angle is 68°. After processing the macrostructure on the titanium alloy surface, it shows directional hydrophobicity after being modified by low surface energy materials. The macro-micro composite structure formed by HV-μEAM realizes a directional hydrophobic surface with contact angles (CA) of 140° (parallel direction) and 130° (perpendicular direction), respectively. This surface has been modified with low surface energy to achieve contact angles of 154° and 143°. The results of the abrasion resistance test show that under the load of 100 g, it retains directional hydrophobicity at a friction distance of 700 mm with 600# sandpaper. The existence of the sub-millimeter macrostructure is the reason for the directionality of surface hydrophobicity. The microstructure can realize the transformation of the titanium alloy surface from hydrophilic to hydrophobic. Under the combined effects of the macro and micro composite structure, the surface of the titanium alloy shows obvious directional hydrophobicity.