tIn this work, the interplay between anion– and pnicogen bond interactions is investigated by ab initiocalculations. Cooperative effects are observed in the studied complexes in which anion– and pnicogenbond interactions coexist. These effects are analyzed in detail in terms of the energetic, geometric, charge-transfer and electron density properties of the complexes. The cooperative energy ranges from −1.8 to−4.1 kcal mol−1. The effect of an anion– bond on a pnicogen bond is more pronounced than that of apnicogen bond on an anion– bond. The enhancing mechanism is analyzed in views with the charge-transfer, electrostatic potential and electron density analysis.