This study conducted longitudinal ultrasonic-assisted milling (UAM) tests and optimized a combination of milling technological parameters to achieve high-quality machining of TC18 titanium alloy. The motion paths of the cutter under the coupled superposition states of longitudinal ultrasonic vibration and end milling were analyzed. Based on the orthogonal test, the cutting forces, cutting temperatures, residual stresses, and surface topographical patterns of TC18 specimens under different UAM conditions (cutting speeds, feeds per tooth, cutting depths, and ultrasonic vibration amplitudes) were examined. The differences between ordinary milling and UAM in terms of machining performance were compared. Using UAM, numerous characteristics (including variable cutting thickness in the cutting area, variable cutting front angles of the tool, and the lifting of the cuttings by the tool) were optimized, reducing the average cutting force in all directions, lowering the cutting temperature, increasing the surface residual compressive stress, and significantly improving the surface morphology. Finally, fish scale bionic microtextures with clear, uniform, and regular patterns were formed on the machined surface. High-frequency vibration can improve material removal convenience, thus reducing surface roughness. The introduction of longitudinal ultrasonic vibration to the end milling process can overcome the limitations of traditional processing. The optimal combination of UAM parameters for titanium alloy machining was determined through the end milling orthogonal test with compound ultrasonic vibration, which significantly improved the surface quality of TC18 workpieces. This study provides insightful reference data for subsequent machining process optimization.