Although Directed Energy Deposition (DED) of Ti–6Al–4V has been widely explored for its mechanical performance, the combined influence of build orientation and surface position (upskin/downskin) on passive film kinetics and fluoride-induced degradation remains largely unexamined. This study addresses this gap by systematically investigating how processing direction and surface thermal history govern microstructure and corrosion behaviour in Laser-Based DED (LB-DED) Ti–6Al–4V. The alloy was fabricated in XY and XZ orientations, and both upskin and downskin surfaces were evaluated. Microstructural characterisation revealed strong anisotropy, with elongated prior-β grains and directional α + β colonies particularly prominent in the XZ orientation. Electrochemical testing in borate buffer showed stable passivity across all conditions, with XY surfaces forming the most compact oxide films. In a more aggressive 2.5% NaF saliva environment, substantial orientation-dependent degradation was observed: XY specimens maintained low corrosion currents and uniform passive layers, whereas XZ downskin exhibited unstable passivation and extensive micro-pitting. These findings demonstrate, for the first time, that the interplay between build orientation and surface position critically dictates passive film defect structure, stability, and fluoride-driven breakdown, providing new mechanistic insight into the corrosion behaviour of DED Ti–6Al–4V relevant to biomedical applications