The thermodynamic properties of gas-phase amino acid ionic liquids (AAILs) containing 20 amino acids ([AA](-)) and 1-ethyl-3-methylimidazolium ([Emim](+)) are studied using a combination of the ab initio method, molecular dynamics simulations, Born-Haber (BH) cycle analysis, and isodesmic reactions. The M06-2X/TZVP method is used to explore the structure and dissociation enthalpies of [Emim] [AA] by considering dispersion interaction, and the MP2/Aug-cc-pVTZ method is used to correct these enthalpies. The vaporization enthalpies of all 20 AAILs are calculated by molecular dynamics simulations, and the gas-phase formation enthalpies (Delta H-f) of the 20 [AA](-) anions and [Emim](+) cation are calculated by the density functional theory/M06-2X method and isodesmic reaction approaches. To obtain the Delta H-f of the AAILs, interconnections in the corresponding BH cycles are evaluated. A systematic study of the 20 [Emim] [AA] ion pairs provides some initial factors contributing to the thermodynamic properties of AAILs: including length of the alkyl chain, interatomic electronic effects, steric repulsion from the cyclic group, and H-bonds formed by functional groups. Generally speaking, the results of this work provide insights into the structure property relationships of not only ILs but also any ionic or molecular substance.