This study explored the process-structure-property (PSP) relationships in Ti-6Al-4V alloys fabricated through direct energy deposition (DED) additive manufacturing. A systematic investigation was conducted to clarify how process variables—specifically, manipulating the cooling rate and energy input by adjusting the laser power and scan speed during the DED process—influenced the phase fractions, pore structures, and the resultant mechanical properties of the samples under various processing conditions. Significant links were found between the controlled process parameters and the structural and mechanical characteristics of the produced alloys. The findings of this research provide foundational knowledge that will drive the development of more effective and precise control strategies in additive manufacturing, thereby improving the performance and reliability of produced materials. This, in turn, promises to make significant contributions to both the advancement of additive manufacturing technologies and their applications in critical sectors.