Titanium alloys get wider applications in different areas due to its excellent mechanical properties. However, poor thermal conductivity and low elastic module of titanium alloy induce high tool wear and make it being one of hard-to-machine materials; especially the segmented chip formation accelerates the diamond tool wear in ultra-precision machining (UPM) of precision parts. This study applies micro-structured surface to improve machinability of titanium alloys in UPM by reducing the chip segmentation induced cutting forces fluctuations. Finite element (FE) model is built to study chip formation mechanism and characterize geometries of segmented chips in orthogonal diamond cutting of Ti6Al4V alloy with the aims at the design of micro-structures array. Turning experiments are conducted to compare cutting force, surface roughness, and tool wear for diamond turning of Ti6Al4V alloy on smooth surface and micro-structured surface. The results show that the FE simulated saw chips agree well with the measured ones. Moreover, the micro-structured surface helps to decrease cutting force, reduce diamond tool wear, and improve surface quality for UPM of titanium alloy. Especially, the new method fabricates micro-grooves array on the machined surface in half-finishing process of UPM without the need of any material pre-processing and extra manufacturing equipment, which can also provide the guidance for efficient and sustainable UPM of titanium alloys parts with high surface quality.