Herein we discuss contributions in the coordination chemistry of azoles and benzazoles, from our and some other research groups. Reactions of polydentate ligands with a diverse combination of donor atoms, as N, O, S, P, with main group and transition metals are commented, as well as their structural analysis. There is a versatile chemistry involved in these compounds, based on a great structural diversity. The ligands promote hypervalent atoms, a wide spectrum of molecular geometries and interactions. The central atoms vary from tri- to octacoordinated. Metallacycles are formed with the participation of the metal ion into the electronic delocalization of the organic π-systems. The high electron density of the ligands, their planar delocalized and rigid framework favor many weak interactions, giving place to macromolecular assemblies based on hydrogen bonds, π-stacking and Lewis acid–base coordination. The compounds offer the possibility of their use as antiparasites drugs, biocides or anticancer substances and in materials science.