AbstractEquilibrium dissociation energies, De, of four series of halogen‐ and hydrogen‐bonded complexes B⋅⋅⋅XCF3 (X=H, Cl, Br and I) are calculated ab initio at the CCSD(T)(F12c)/cc‐pVDZ‐F12 level. The Lewis bases B involved are N2, CO, PH3, C2H2, C2H4, H2S, HCN, H2O and NH3. Plots of De versus NB, where the NB are the nucleophilicities assigned to the Lewis bases previously, are good straight lines through the origin, as are those for the corresponding set of complexes B⋅⋅⋅XCl. The gradients of the De versus NB plots define the electrophilicities EXCF3 and EXCl of the various Lewis acids. The determined values are: EXCF3=2.58(22), 1.40(9), 2.15(2) and 3.04(9) for X=H, Cl, Br and I, respectively, and EXCl=4.48(22), 2.31(9), 4.37(27) and 6.06(37) for the same order of X. Thus, it is found that, for a given X, the ratio EXCl/ EXCF3 is 2 within the assessed errors, and therefore appears to be independent of the atom X and of the type of non‐covalent interaction (hydrogen bond or different varieties of halogen bond) in which it is involved. Consideration of the molecular electrostatic surface potentials shows that De and the maximum positive electrostatic potential σmax (the most electrophilic region of XCF3 and XCl, which lies on the symmetry axes of these molecules, near to the atom X) are strongly correlated.