This paper will deal with recent results regarding voltammetric and amperometric determinations of micromolar and submicromolar concentrations of various environmentally important biologically active inorganic and organic substances using solid and paste amalgam electrodes, which can be environmentally friendly alternatives to mercury electrodes. Attention will be paid to amalgam electrodes either in batch analysis or in flow liquid systems (especially HPLC or flow-injection analysis with electrochemical detection). Silver amalgam electrodes can be used in voltammetric and amperometric analysis as an alternative to mercury electrodes. Other solid amalgam electrodes (e.g., CuSAE, AuSAE) are convenient for specific purposes, where properties of the metal, of which the solid amalgam consists, are employed. Different types of amalgam electrodes have been used as highly sensitive tools for the detection of DNA strand breaks, as sensors for DNA cleaving substances, for the detection of enzymatic or chemical DNA cleavage in solution or at the electrode surface, as a sensor for DNA nicking substances and for the detection of DNA strand breaks induced by ionizing radiation.