Wet-chemical methods, under rigorous air-free conditions, were used to synthesize single-crystalline 10 nm diameter PbSe nanowires (NWs), and electric-field, directed assembly was employed to align NW arrays to form the semiconducting channels of field-effect transistors (FETs). Electrical measurements revealed as-aligned NWs in bottom, gold, contact FETs are predominantly p-type ambipolar, consistent with the presentation of small barriers to electron and hole injection for this low band gap semiconductor. Exposing the NW FET to UV-ozone p-doped the NWs, illustrating the sensitivity of PbSe to oxygen, but controlled oxidation allowed the fabrication of unipolar p-type FETs. Selectively exposing the contact region of as-aligned NW FETs to low to moderate concentrations of hydrazine, commonly used to n-dope nanocrystal and NW devices, switched the predominantly p- to n-type ambipolar behavior as if the entire NW channel was exposed. At these hydrazine concentrations, charge transfer doping the metal-semiconductor interface dominates the FET characteristics. Only upon exposing the NW FETs to high hydrazine concentrations did charge transfer doping of the NW channel overcome the large intrinsic, thermally generated carrier concentration of this low band gap material, modulating the NW carrier concentration and forming unipolar n-type FETs. Pulling low vacuum removed surface hydrazine returning the predominantly p-type ambipolar FET behavior. Doping and dedoping with hydrazine were repeatedly reversible. By applying surface modification to n- and p-dope PbSe NW FETs, we fabricated the first PbSe NW inverters, demonstrating the promise of these nanostructured materials in integrated circuits.