This work introduces a method for co-localized multi-modal imaging of sub-μm features in an additively manufactured (AM) titanium alloy. Ti-6Al-4V parts manufactured by electron beam melting powder bed fusion were subjected to hot isostatic pressing to seal internal porosity and machined to remove contour–hatch interfaces. Electron microscopy and atomic force microscopy-based techniques (electron backscatter diffraction and scanning Kelvin probe force microscopy) were used to measure and categorize the effects of crystallographic texture, misorientation, and phase content on the relative differences in the Volta potential of α-Ti and β-Ti phases. Given the tunability of additive manufacturing processes, recommendations for texture and phase control are discussed. In particular, our findings indicate that the potential for micro-galvanic corrosion initiation can be regulated in AM Ti-6Al-4V parts by minimizing both the total area of {111} prior-β grains and the number of contact points between {111} β grains and α laths that originate from {001} prior-β grains.