While core-shell wire-based devices offer a promising path toward improved optoelectronic applications, their development is hampered by the present uncertainty about essential semiconductor properties along the three-dimensional (3D) buried p-n junction. Thanks to a cross-sectional approach, scanning electron beam probing techniques were employed here to obtain a nanoscale spatially resolved analysis of GaN core-shell wire p-n junctions grown by catalyst-free metal-organic vapor phase epitaxy on GaN and Si substrates. Both electron beam induced current (EBIC) and secondary electron voltage constrast (VC) were demonstrated to delineate the radial and axial junction existing in the 3D structure. The Mg dopant activation process in p-GaN shell was dynamically controlled by the ebeam exposure conditions and visualized thanks to EBIC mapping. EBIC measurements were shown to yield local minority carrier/exciton diffusion lengths on the p-side (∼57 nm) and the n-side (∼15 nm) as well as depletion width in the range 40-50 nm. Under reverse bias conditions, VC imaging provided electrostatic potential maps in the vicinity of the 3D junction from which acceptor Na and donor Nd doping levels were locally determined to be Na = 3 × 10(18) cm(-3) and Nd = 3.5 × 10(18) cm(-3) in both the axial and the radial junction. Results from EBIC and VC are in good agreement. This nanoscale approach provides essential guidance to the further development of core-shell wire devices.