Recently, owing to the large surface-area-to-volume ratio of nanowires (NWs), manipulation of their surface states becomes technologically important and being investigated for various applications. Here, an in-situ surfactant-assisted chemical vapor deposition is developed with various chalcogens (e.g. S, Se and Te) as the passivators to enhance the NW growth and to manipulate the controllable p-n conductivity switching of fabricated NW devices. Due to the optimal size effect and electronegativity matching, Se is observed to provide the best NW surface passivation in diminishing the space charge depletion effect induced by the oxide shell and yielding the less p-type (i.e. inversion) or even insulating conductivity, as compared with S delivering the intense p-type conductivity for thin NWs with the diameter of similar to 30 nm. Te does not only provide the surface passivation, but also dopes the NW surface into n-type conductivity by donating electrons. All of the results can be extended to other kinds of NWs with similar surface effects, resulting in careful device design considerations with appropriate surface passivation for achieving the optimal NW device performances.