GaAs epilayers grown on Si by metalorganic chemical vapor deposition (MOCVD) using an ultrathin a-Si buffer layer were characterized by deep-level transient spectroscopy (DLTS). Six electron traps with activation energies of 0.79, 0.67, 0.61, 0.55, 0.53 and 0.32 eV below the conduction band were determined by fitting the experimental spectra. Two of the levels, C (0.61 eV) and F (0.32 eV), were first detected in GaAs epilayers on Si and identified as the metastable defects M3 and M4, respectively. In order to improve the quality of GaAs/Si epilayers, another GaAs layer was grown on the GaAs/Si epilayers grown using MOCVD. The deep levels in this regrown GaAs epilayer were also studied using DLTS. Only the EL2 level was found in the regrown GaAs epilayers. These results show that the quality of the GaAs epilayer was greatly improved by applying this growth process.