Exposure of GaAs crystals to solutions of organic thiols resulted in substantial reductions in nonradiative GaAs surface recombination rates. This process yielded improvements in steady state photoluminescence signals that were comparable to those obtained after a Na2S⋅9H2O (aqueous) treatment. Use of a series of thiols indicated that the chemically important surface electrical trap levels behaved as a polarizable, electron deficient center. X‐ray photoelectron spectroscopy indicated that the thiols did not remove excess As0nor form detectable levels of As2S3‐like phases, implying that neither of these factors is required for effective surface passivation chemistry.