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_z 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 π 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.