The high chemical reactivity and low thermal conductivity of titanium-alloys are the main reasons for not using PCD tools in machining of Ti-alloys. The aim of this recent research study on three different PCD grades involving tool life and wear development is to understand the role of characteristic PCD properties (i.e. grain size, its distribution and cobalt content) in machining of β-titanium alloy (Ti5Al5V5Mo3Cr). The results show a clear relationship between the characteristic PCD properties and the development of crater wear while abrasive wear does not play a dominant role in the evaluation of tool performance. Within a specific cutting data window PCD tools can contribute to improved machinability of Ti5Al5V5Mo3Cr compared to commonly used carbide tools. Different advanced analysis methods such as scanning electron microscopy (SEM) and (scanning) transmission electron microscopy ((S)TEM) in combination with energy dispersive X-ray spectroscopy (EDXS) and electron energy loss spectroscopy (EELS) have been applied to understand the basic wear mechanisms on the atomic scale. The performance results clearly show that the design of the PCD grade is one of the main factors for improving performance of the diamond tool in terms of wear development and tool life. Based on the presented results the crater wear development can be explained by atomistic processes.