We report, for the first time, the synthesis of the high-quality p-type ZnO NWs using a simple chemical vapor deposition method, where phosphorus pentoxide has been used as the dopant source. Single-crystal phosphorus doped ZnO NWs have their growth axis along the 001 direction and form perfect vertical arrays on a-sapphire. P-type doping was confirmed by photoluminescence measurements at various temperatures and by studying the electrical transport in single NWs field-effect transistors. Comparisons of the low-temperature PL of unintentionally doped ZnO (n-type), as-grown phosphorus-doped ZnO, and annealed phosphorus-doped ZnO NWs show clear differences related to the presence of intragap donor and acceptor states. The electrical transport measurements of phosphorus-doped NW FETs indicate a transition from n-type to p-type conduction upon annealing at high temperature, in good agreement with the PL results. The synthesis of p-type ZnO NWs enables novel complementary ZnO NW devices and opens up enormous opportunities for nanoscale electronics, optoelectronics, and medicines.