The antidiabetic drug metformin (MET) is one of a group of emerging pharmaceutical drug contaminants in the wastewater treatment plants. The electrochemical behaviour of MET−Cu(II) complex by differential pulse and square wave voltammetry, in a wide pH range, at a glassy carbon electrode modified with a carbon black dihexadecylphosphate film (CB−DHP/GCE), was investigated. The MET−Cu(II) complex oxidation showed one pH‐dependent process, which leads to the formation of an oxidation product, being oxidized at a lower potential. The electroanalytical MET−Cu(II) complex detection limit, LOD=0.63 μM, and quantification limit, LOQ=2.09 μM, were obtained, and the MET−Cu(II) complex determination in wastewater samples collected from a senior residence effluent, using the CB−DHP/GCE, was achieved. Considering MET toxicity, the electrochemical evaluation of MET−dsDNA interaction, in incubated solutions and using dsDNA‐electrochemical biosensors, following the changes in the oxidation peaks of guanosine and adenosine residues electrochemical currents, was also investigated. The MET−dsDNA interaction mechanism, for shorter times, occurs by the binding of MET molecules in the minor grooves of the dsDNA, and for long times, the stabilization of the MET−dsDNA complex, causing a local distortion and/or unwinding of dsDNA morphology, is described. However, MET did not promote DNA oxidative damage.