Protonation of gabapentin was studied using corona discharge ion mobility spectrometry with two types of reactant ions at temperature of 200°C. It was found that at elevated temperatures, ionization of gabapentin proceeds via two channels, including the protonation and reactant ion attachment, in the presence of both hydronium and ammonium reactant ions. The effect of the sample concentration on the relative intensity of product ion peaks was also studied. It turned out that in high concentrations, in addition to the protonation of gabapentin, binding of the reactant ion and the formation of proton-bound dimer also occurred, while in low concentrations, the only product of the ionization process is protonated gabapentin. Density functional theory (DFT) with B3LYP and M062X functionals employing the same basis set 6-311++G(d,p) was used to extend the experimental findings. The structures of the several conformers of neutral and protonated gabapentin were obtained. Based on them, topical proton affinity and topical gas-phase basicity of gabapentin were calculated for selected conformers. The attachment of reactant ions to neutral gabapentin and formation of proton-bound dimer were thermodynamically studied.