High-quality CdS nanowires with uniform Sn doping were synthesized using a Sn-catalyzed chemical vapor deposition method. X-ray diffraction and transmission electron microscopy demonstrate the single crystalline wurtzite structure of the CdS/Sn nanowires. Both donor and acceptor levels, which originate from the amphoteric nature of Sn in II-VI semiconductors, are identified using low-temperature microphotoluminescence. This self-compensation effect was cross examined by gate modulation and temperature-dependent electrical transport measurement. They show an overall n-type behavior with relatively low carrier concentration and low carrier mobilities. Moreover, two different donor levels due to intrinsic and extrinsic doping could be distinguished. They agree well with both the electrical and optical data.