Due to the large surface-to-volume ratio, surface trap states play a dominant role in the optoelectronic properties of nanoscale devices(1-6). Understanding the surface trap states allows us to properly engineer the device surfaces for better performance. But characterization of surface trap states at nanoscale has been a formidable challenge using the traditional capacitive techniques based on metal-insulator-semiconductor (MIS) structures(7) and deep level transient spectroscopy (DLTS)(8-11). Here, we demonstrate a simple but powerful optoelectronic method to probe the density of nanowire surface trap states to the limit of a single trap state. Unlike traditional capacitive techniques (Fig1a), in this method we choose to tune the quasi-Fermi level across the bandgap of a silicon nanowire photoconductor, allowing for capture and emission of photogenerated charge carriers by surface trap states (Fig1b). The experimental data show that the energy density of nanowire surface trap states is in a range from 10 9 cm -2 /eV at deep levels to 10 12 cm -2 /eV in the middle of the upper half bandgap. This optoelectronic method allows us to conveniently probe trap states of ultra-scaled nano/quantum devices at extremely high precision.To understand this method, let us use p-type semiconductors as an example. A highly doped ptype semiconductor has an extremely high concentration of holes but a very low concentration of electrons. Under illumination, excess electrons and holes are generated in the conduction and valence band, respectively. At small injection condition, these excess carriers are negligibly low in concentration compared to the majority holes, but often orders of magnitude larger than the minority electrons. Consequently, the quasi-Fermi level of electrons ( ) shifts away significantly from the Fermi level at equilibrium ( ), while the quasi-Fermi level of holes ( ) remains nearly unchanged as , as shown in Fig.1b. In general, the shift of quasi-Fermi levels leads to filling the trap states below (but above ) with electrons, and those above (but below ) with holes. Clearly, for a highly doped p-type semiconductor at small injection condition, only the minority electrons get involved in the capture-emission process of trap states. For every photogenerated electron captured by trap states, there is one corresponding hole remaining in the valence band to contribute to photoconductance. The shift of will allow a large number of electrons to be trapped if the density of trap states, at deep levels in particular, is high, leading to the giant gain in photoconductance that has been widely observed(1-3).