The reactions of CS2 captured by intramolecular geminal G13/P-based (G13 = group 13 elements) and Ga/G15-based (G15 = group 15 elements) frustrated Lewis pairs have been theoretically examined by using density functional theory (DFT) computations. With regard to the nine FLP-related compounds, our DFT calculated results reveal that only Al/P-Rea and Ga/P-Rea can kinetically and thermodynamically precede the energetically feasible combination reactions with CS2 to form the five-membered heterocyclic adducts. Our activation strain model analyses on the nine aforementioned model molecules indicate that the atomic radius of the Lewis acceptor (G13) and the Lewis donor (G15) plays a role in controlling their barrier heights to obtain good orbital overlaps among G13/P-Rea, Ga/G15-Rea, and CS2. Our theoretical observations based on the energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) approach strongly indicate that the donor-acceptor bonding (i.e., singlet-singlet bonding) rather than the electron-sharing bonding (i.e., triplet-triplet bonding) plays a central role in determining the bonding conditions of the transition states, G13/P-TS and Ga/G15-TS. In addition, the theoretical evidence obtained by the frontier molecular orbital theory and EDA-NOCV analyses reveals that the best description for the bonding natures of the combination reactions of intramolecular geminal G13/P-Rea and Ga/G15-Rea with CS2 is the lone pair(G15) → p-π*(C) interaction rather than the p-π*(G13) ← p-π(S) interaction. Moreover, our present DFT computations concerning the calculated structures and corresponding relative energetics of the stationary points connected with the aforementioned sophisticated approaches are in accordance with the Hammond postulate.