Prior studies in metal additive manufacturing (AM) of parts have shown that various AM methods and post-AM heat treatment result in distinctly different microstructure and machining behavior when compared with conventionally manufactured parts. There is a crucial knowledge gap in understanding this process-structure-property (PSP) linkage and its relationship to material behavior. In this study, the machinability of metallic Ti-6Al-4V AM parts was investigated to better understand this unique PSP linkage through a novel data science-based approach, specifically by developing and validating a new machine learning (ML) model for material characterization and material property, that is, machining behavior. Heterogeneous material structures of Ti-6Al-4V AM samples fabricated through laser powder bed fusion and electron beam powder bed fusion in two different build orientations and post-AM heat treatments were quantitatively characterized using scanning electron microscopy, electron backscattered diffraction, and residual stress measured through X-ray diffraction. The reduced dimensional representation of material characterization data through chord length distribution (CLD) functions, 2-point correlation functions, and principal component analysis was found to be accurate in quantifying the complexities of Ti-6Al-4V AM structures. Specific cutting energy was the response variable for the Taguchi-based experimentation using force dynamometer. A low-dimensional S-P linkage model was established to correlate material structures of metallic AM and machining properties through this novel ML model. It was found that the prediction accuracy of this new PSP linkage is extremely high (>99%, statistically significant at 95% confidence interval). Findings from this study can be seamlessly integrated with P-S models to identify AM processing conditions that will lead to desired material behaviors, such as machining behavior (this study), fatigue behavior, and corrosion resistance.