The present study explores the near atomic scale spatial distributions of substitutional alloying elements (aluminium and vanadium) and interstitial impurities (oxygen and carbon) in the microstructures of Ti-6Al-4V and its boron modified counterpart (Ti-6Al-4V-0.1B) alloys using transmission electron microscopy (TEM) and atom probe tomography (APT) techniques. The latter alloy possesses zero solubility of boron in α-Ti and high oxygen concentration around TiB particles. The results suggest that aluminium and vanadium atoms enrich α and β phases, respectively due to strong elemental partitioning between these phases, to an extent that the atomic scale concentrations of various elements considerably differ from the bulk compositions of the two alloys. Furthermore, oxygen atoms are preferentially distributed within the α phase where other interstitial impurities (carbon) also segregate. Substitutional aluminium atoms share an inverse interrelation with interstitial oxygen atoms while vanadium atoms reside besides the impurity-rich regions for both the alloys. The size differences for these elements (substitutional vs. interstitial) with host titanium atoms and related lattice distortion is (partially) held responsible for the atomic scale elemental distributions and the observed interrelations within the α phase. These arguments are further substantiated from DFT results previously obtained for Ti-6Al-4V alloy.