The stability and electron density topology of catechol complexes (dimers and tetramer) were studied using the MPW1B95 functional. The QTAIM analysis shows that both dimers (face to face and C-H/pi one) display a different electronic origin. The formation of the former is accompanied by a significant change in the values of atomic electron dipole and quadrupole components, flattening the most diffuse part of the electron density distribution toward the molecular plane. A small electron population transfer is observed between catechol monomers connected by C-H/pi interactions, whose QTAIM characterization does not differ from that of a weak hydrogen bond. Cooperative effects in the tetramer on binding energies are small and negligible for bond properties and charge transfer. Nevertheless, they are significant oil atomic electron populations.