A nanowire comprises a polar semiconductor material that is compositionally graded along the nanowire from a first end to a second end to define a polarization doping profile along the nanowire from the first end to the second end. The polar semiconductor material may comprise a group IH-nitride semiconductor, such as an alloy of GaN and AlN, or an alloy of GaN and InN. Such nanowires may be formed by nucleating the first ends on a substrate, growing the nanowires by depositing polar semiconductor material on the nucleated first ends on a selected growth face, and compositionally grading the nanowires during growth to impart the polarization doping. The direction of the compositional grading may be reversed during the growing of the nanowires to reverse the type of the imparted polarization doping. In some embodiments, the reversing forms n/p or p/n junctions in the nanowires.