Abstract An application of the quantum chemical modeling allowed to investigate the nature of the field/inductive substituent effect (SE). For this purpose, series of X - tert -butyl··· tert -butane (TTX) complexes (where X = NMe 2 , NH 2 , OH, OMe, Me, H, F, Cl, CF 3 , CN, CHO, COMe, CONH 2 , COOH, NO 2 , NO) were studied. A starting distance between central carbon atoms in substituted and unsubstituted fragments of TTX, d C1–C4 , was the same as the distance C1–C4 in X -substituted bicyclo[2.2.2]octane (BCO), where the SE acts both via bonds and via space. A strength of interaction between substituted and unsubstituted components of TTX was described by deformation and interaction energies. The substituent effect on electronic structure through the bonds and the space was characterized using charge of the substituent active region (cSAR) approach. The comparison of the SE characteristics obtained for alicyclic BCO and for TTX complexes document a significantly stronger field/inductive effect through bonds than through space.