The gas-phase hydride abstraction of methylamine with Cu+(1S) is theoretically investigated by using density functional theory. Geometries for all the stationary points involved are fully optimized at both the B3LYP/6-311++G(d,p) and B3LYP/6-311++G(3df,2p) levels and the reaction is analyzed in terms of the topology of potential energy surface. Approach of Cu+towards methylamine could form either “classical” N or “nonclassical” η1-methyl-H attached complex with the former being the global minimum. Both complexes are found to be key intermediates for the hydride abstraction, which could transfer into each other via two parallel routes, i.e., concerted metal movement and stepwise C–H activation-rearrangement. A charge-transfer process is detected for the “nonclassical” complex converting to a precursor species (CuH–NH2CH2+), which accounts for the final products by a nonreactive dissociation.