Titanium aluminides are of great technological interest because of their attractive mechanical properties. Mechanical milling/alloying is a promising powder metallurgical technique, which can achieve ultrafine, uniform and manipulable microstructures. In this study, we employed a recently revisited discus mill to produce a composite Ti-(50-57) at.%Al powder feedstock, which is suitable for hot consolidation to produce bulk cathode targets for physical vapour deposition (PVD) coatings. The effects of milling time, quantity of process control agent (PCA) and discus-to-powder weight ratio (DPR) on the microstructure evolution of the attendant Ti/Al composite powder were investigated in detail. It was found that to produce Ti/Al composite powders with a fine particle size and a uniform microstructure, the practicable processing parameters should be 2 or 3% isopropanol addition as PCA, 12 h of milling time and at least 13:1 DPR weight ratio. Cathode targets were produced by hot isostatic pressing (HIPing) the as-milled powders. The targets were then used to produce a PVD TiAlN coating which had an average microhardness of 2400 HV.