The vacuum ultraviolet laser-excited photoion-pair formation spectrum of CH3Br has been measured under high resolution in the threshold region. The (2 + 1) and (3 + 1) resonance-enhanced multiphoton ionization spectra in the same energy region are also reported. By comparison of the spectra in this and a more extended region, resonances in the photoion-pair formation spectrum are assigned to p and f Rydberg states. It is concluded that all the structure in the photoion-pair formation spectrum near threshold can be accounted for by members of the Omega = 0 subset of Rydberg states that act as doorway states to the ion channel.