A theoretical gas-phase “ligand-free” or “electron pair affinity” (EPA) approach, based on CCSD(T)/(SDB-)cc-pVTZ//MP2/(SDB-)cc-pVTZ electronic structure calculations, is introduced as a possible means for determining Lewis acidity trends among planar EX3 0/+ (E=B, C, Al, Si; X=F, Cl, Br, I) species. In this treatment, the free electron pair is considered to be an extreme Lewis base. The calculated EPA values are compared with experimental Lewis acidities, previously calculated fluoride ion affinity (FIA) and hydride ion affinity (HA) trends, and are found to exhibit reasonable correlations in all cases. The bonding in the planar and trigonal pyramidal conformations of EX3 0/+ and of the trigonal pyramidal Lewis base EX3 2−/− anions are assessed by use of natural bond orbital (NBO) and natural resonance theory (NRT) analyses. The NBO charges of the CX3 + (X=Cl, Br, I, OTeF5) cations are shown to correlate with the cation–anion and cation–solvent contacts in the recently determined crystal structures of [CCl3][Sb(OTeF5)6], [CBr3][Sb(OTeF5)6]·SO2ClF, [CI3][Al(OC(CF3)3)4], and [C(OTeF5)3][Sb(OTeF5)6]·3SO2ClF and known fluoro-carbocation structures. Topological electron localization function (ELF) basin lobe isosurfaces and volumes are used to rationalize the Lewis acidity trends and bond ionicities of the EX3 0/+ species, and Lewis basicities of the EX3 2−/− species.