The electrochemistry of the codeposition of Se(IV) and Cu2+ at a hanging-mercury-drop electrode has been studied in detail in 0.1 M HClO4 or HCl solutions. Films consisting of Cu2Se are formed and the cathodic stripping of these films results in a single well-defined stripping peak which is suitable for analytical applications. The cuprous selenide is most probably formed by an exchange reaction between HgSe or Se(Hg) at low Se(IV) concentrations, and the copper amalgam. The stripping of the Cu2Se film is compared with that of Se(Hg) and HgSe with respect to its sensitivity and versatility for different voltammetric techniques and evaluation procedures. Linear sweep voltammetry in combination with stripping charge measurement is recommended for the determination of selenium.