Single-crystalline rock-salt PbS nanowires (NWs) were synthesized using three different routes; the solvothermal, chemical vapor transport, and gas-phase substitution reaction of pre-grown CdS NWs. They were uniformly grown with the  or ,  direction in a controlled manner. In the solvothermal growth, the oriented attachment of the octylamine (OA) ligands enables the NWs to be produced with a controlled morphology and growth direction. As the concentration of OA increases, the growth direction evolves from the  to the higher surface-energy  and  directions. In the synthesis involving chemical vapor transport and the substitution reaction, the use of a lower growth temperature causes the higher surface-energy growth direction to change from  to . We fabricated field effect transistors using single PbS NW, which showed intrinsic p-type semiconductor characteristics for all three routes. For the PbS NW with a thinner oxide layer, the carrier mobility was measured to be as high as 10 cm2V−1s−1.