The fatigue behavior of additively manufactured (AM) structural parts is sensitive to the surface and near-surface material conditions. Chemical post-processing surface treatments can be used to improve the surface condition of AM components, including complex geometries with surfaces difficult to access. In this work, surfaces of electron beam powder bed fusion (EB-PBF) produced Ti–6Al–4V were subject to two different chemical post-processing surface treatments, chemical milling and Hirtisation. As-built and machined surfaces, as well as hot isostatic pressing (HIP), treated conditions were also investigated. Fatigue testing was carried out in four-point bending. The investigation focused on the relationship between fracture mechanisms and fatigue life through fractographic study. It was found that a majority of fractures were initiated at internal surface-near defects or defects on the surface. Chemical post-processing was found to smoothen the surface but to leave a surface waviness. Material removal during post-processing could open up internal defects to the treated surface. In HIP-treated specimens, fractures initiated at defects open to the surface. Despite post-processing increasing the mean life of fatigue specimens, no significant improvements in the lowest tested life were observed for any specimen condition.