Directed Energy Deposition Additive Manufacturing (DED-AM) is transformative for the production of larger, geometrically complex metallic components. However, the mechanical properties of titanium alloy DED-AM components do not always reach their full potential due to microstructural features including porosity and regions of lack of fusion. Using in situ and operando synchrotron X-ray imaging we gain insights into key laser-matter interaction and microstructural feature formation mechanisms during DED-AM of Ti-6242. Analysis of the process conditions reveals that laser power is dominant for build efficiency while higher traverse speed can effectively reduce lack of fusion regions. We also elucidate the mechanisms underlying several physical phenomena occurring during the deposition of titanium alloys, including the formation of a saddle-shaped melt pool and pore pushing. The findings of this work clarify the transient kinetics behind the DED-AM of titanium alloys and can be used as a guide for optimising industrial additive manufacturing processes.