The water‐exchange mechanisms of [Zn(H2O)4(L)]2+⋅2 H2O (L=imidazole, pyrazole, 1,2,4‐triazole, pyridine, 4‐cyanopyridine, 4‐aminopyridine, 2‐azaphosphole, 2‐azafuran, 2‐azathiophene, and 2‐azaselenophene) have been investigated by DFT calculations (RB3LYP/6‐311+G**). The results support limiting associative reaction pathways that involve the formation of six‐coordinate intermediates [Zn(H2O)5(L)]2+⋅H2O. The basicity of the coordinated heterocyclic ligands shows a good correlation with the activation barriers, structural parameters, and stability of the transition and intermediate states.