This study demonstrates the potential of the electrochemical methods for the characterization of dissolved organic matter (DOM) in the drainage water of hydroameliorated agricultural areas. A study of drainage water could lead to a better understanding of the distribution and fate of terrestrial DOM in the freshwater systems. We have applied the voltammetric techniques which were developed by our group for the characterization of organic matter in the natural waters in general. Studied samples were collected in the experimental amelioration fields in the Sava river valley (45 ° 33′ 52″ N/16° 31′ 33″ E, 100 m above sea level), in the hydroameliorated agricultural areas in Croatia. The rough characterization of the type, nature and reactivity of DOM was done through the study of surface activity (SA) of dissolved organic carbon (DOC), copper complexing capacity (CuCC) and apperent stability constants, and measurements of organic and inorganic reduced sulfur species (RSS) fractions. The results confirm that the electrochemical approach gives a valuable and comprehensive insight into physicochemical characteristics of DOM in the drainage water and could be successfully applied to temporal studies in different terrestrial ecosystem.