The crystallographic and compositional structure of heterostructured semiconductor nanowires has been studied by means of transmission electron microscopy. The native geometry of the studied InP-GaAs nanowires (80–100 nm in diameter) is in general too thick for reliable high-resolution TEM imaging. Nano Beam Electron Diffraction (NBED) is shown to be a powerful technique to reveal strain near the interface of compositional change in heterostructured semiconductor nanowires. Furthermore, the relative orientation of the nanowires is studied by means of NBED revealing the nanowires to be very flexible. NBED proves to be a good alternative to convergent beam electron diffraction and electron backscatter diffraction in terms of crystal orientation determination and mapping.