The photoelectron spectra of the negative ions, CH3NH- and (CH3)(2)N-, as well as the anion complexes, H-(CH3NH2) and (CH3)(2)N-[(CH3)(2)NH] have been measured. The adiabatic electron affinities of CH3NH and (CH3)(2)N were determined to be 0.432 +/- 0.015 and 0.504 +/- 0.030 eV, respectively. The vertical detachment energies of H-(CH3NH2) and (CH3)(2)N-[(CH3)(2)NH] were determined to be 1.157 +/- 0.025 and 1.1 +/- 0.1 eV, respectively, while the anion-neutral dissociation energies of H-(CH3NH2) and (CH3)(2)N-[(CH3)(2)NH] were found to be 0.40 and 0.6 eV, respectively. These species are compared with their unmethylated counterparts, NH2-, H-(NH3), and NH-,(NH3). (C) 2002 Eisevier Science B.V. All rights reserved.