Our laboratory started research on tetraazaporphyrins in the middle of the 1970s. Before our works there was no information in the literature about coordination and ionization properties of these compounds, formation of their metal complexes or their state and behavior in proton-donating and proton-acceptor media. We carried out the first studies of the coordination and acid-base properties of unsubstituted tetraazaporphine [1], its octaphenyl [2] and tetra(tetramethylene)-[3] substituted derivatives. In this micro-review we summarize our works on the peripheral functionalization of unsubstituted porphyrazines and on their acid-base and coordination properties.