The electronic structure and geometries of (Z)- and (E)-H-CON-N+(CH3)(3) have been examined at two levels of theory: B3LYP (basis sets 6-311+G(d,p), 6-311++G(d,p), and 6-311G(3df,3pd)) and MP2(full)/6-311++G(d,p). The (Z) conformation about the C(O)N--(-) bond is thermodynamically preferred over the (E) configuration. Natural bond orbital calculation locates one lone pair of the N- in the HOMO, which is the p, natural hybrid orbital (perpendicular to the O=CN-N+ plane). The second lone pair (of lower energy) of N- occupies the HOMO-3, which is the natural hybrid orbital sp(1.12) (sp(1.01) for the (E) conformation, sp(1.74) in the rotational transition state). The carbonyl pi bond is the HOMO-2. The charge-transfer ability of the negative nitrogen in H-CON-N+(CH3)(3) is more powerful than that of the neutral amidic nitrogen in dimethylformamide. The following facts convincingly sustain this view: (1) the higher rotational barrier (stronger C-N- bond) in the case of H-CON-N+(CH3)3, (2) natural resonance theory analysis predicts almost equal weights for the (Z)-H-C(=O)N-N+(CH3)(3) and the (Z)-H-C(O-)=NN+(CH3)(3) canonical resonance structures whereas the weight of the HCON(CH3)(2) structure is almost twice as large as that of HC(O-)=N+(CH3)(2), and (3) the second-order perturbation stabilization, as a result of the donor (N-)/acceptor (carbonyl) interaction, is 101.3 kcal/mol for H-CON-N+(CH3)(3) and only 64.4 kcal/mol for dimethylformamide.