Synthesis, electrochemistry and spectroscopic techniques for five zinc(II) coordination complexes with a combination of tetradentate amines 1,4-bis(3-aminopropyl)piperazine (bapi), triethylenetetramine (tet) and 1,1,4,7,10,10-hexamethyltriethylenetetramine (mtet) and thiodiacetic (tdaH2) or 1,3,5-benzenetricarboxylic acid (btcH3) are described. These complexes of general formulas [Zn2(L)2(µ-tda)](ClO4)2 and [Zn3(L)3(µ-btc)](ClO4)3, where L = bapi, tet, mtet, have been studied in water solution. Their stability has been studied by electrochemical methods (cyclic voltammetry and differential pulse voltammetry) by using the hanging mercury drop electrode. There were also studied interactions of zinc(II) complexes with UV radiation assessed by fluorescence spectroscopy. It was found out that three complexes (Zn3(bapi)3(µ-btc)](ClO4)3; Zn3(tet)3(µ-btc)](ClO4)3; Zn3(mtet)3(µ-btc)](ClO4)3), after three minutes of UV irradiation became fluorescently active (λEm = 400 nm) and fluorescence increased after each interval of UV irradiation.