High level ab initio calculations have been performed to investigate the mechanism of the ion-molecule reaction NH3+C2H2+. Three channels, covalent complex formation (CC), proton transfer (PT), and charge transfer (CT) have been studied. Among the two pathways found for the PT channel, one leads the reactants NH3+C2H2+ to NH4++C2H((2) Pi) through a moderately bound complex without any barrier, and the other leads NH3++C2H2 to the H-atom transferred products NH4++C2H((2) Sigma(+)) with a modest barrier. These findings support the fast "stripping" mechanism proposed by Anderson et al. As to the CC channel, several isomers of C2H5N+ and the isomerization transition states have been located. No significant barrier relative to the reactants has been found on either the ground or the (2)A " excited state. To rationalize the experimental fact that no CC channel products have been observed; it is argued that the: reactants NH3+C2H2+ adiabatically to excited states of covalent C2H5N+ species, whose formation requires significant alternation of the C2H2+ geometry and electronic structure. Therefore, the system is most likely to follow the PT or the CT channel instead of visiting the CC channel. For the CT channel, limited potential energy surface scans of the three electronic states (1,2 (2)A' + (2)A ") indicate that CT at different approach angles or between electronic states of different symmetries (A'-->A', A "-->A') may produce final products of different characteristics, and might account for the two pathways proposed by Anderson et al.