σ-Hole and lone-pair (lp)-hole interactions of aerogen oxides with Lewis bases (LB) were comparatively inspected in terms of quantum mechanics calculations. The ZO
n
⋯ LB complexes (where Z = Kr and Xe,
n
= 1, 2, 3 and 4, and LB = NH
3
and NCH) showed favourable negative interaction energies. The complexation features were explained in light of σ-hole and lp-hole interactions within optimum distances lower than the sum of the respective van der Waals radii. The emerging findings outlined that σ-hole interaction energies generally enhanced according to the following order: KrO
4
⋯ < KrO⋯ < KrO
3
⋯ < KrO
2
⋯LB and XeO
4
⋯ < XeO⋯ < XeO
2
⋯ < XeO
3
⋯LB complexes with values ranging from –2.23 to –12.84 kcal mol
−1
. Lp-hole interactions with values up to –5.91 kcal mol
−1
were shown. Symmetry-adapted perturbation theory findings revealed the significant contributions of electrostatic forces accounting for 50–65% of the total attractive forces within most of the ZO
n
⋯LB complexes. The obtained observations would be useful for the understanding of hole interactions, particularly for the aerogen oxides, with application in supramolecular chemistry and crystal engineering.