We perform a deep level transient spectroscopy (DLTS) measurement of the band‐gap energy distribution of the trivalent silicon defects (Pbcenters) on as‐oxidized ⟨100⟩ silicon wafers. By comparison with the ⟨111⟩ silicon surface, we isolate the energy distribution of thePb1center. Its acceptor level is found at 0.42 ± 0.02 eV from the conduction band while the acceptor level for the ⟨100⟩Pb0center is found at 0.22 ± 0.01 eV, a value smaller than at the ⟨111⟩ surface (0.33 ± 0.01 eV). We obtain new results about the capture cross sections of the ⟨100⟩Pbcenters by energy‐resolved DLTS trap filling experiments. The electron capture cross section of ⟨100⟩Pb1is determined for the first time (5×10−16cm2), while the electron capture cross section for ⟨100⟩ Pb0(8×10−15cm2) is found to be in agreement with earlier results.