Uranyl, UO(2)(2+), was electrochemically determined by a phosphate based self-assembled monolayer. A pretreated gold electrode with 2-mercatpoethanol was chemically modified by POCl(3) or POBr(3) to obtain the surface phosphate active sites. The different stages were characterized by reflection-absorption Fourier transform-infrared (FT-IR) spectroscopy, capacity, and X-ray photoelectron spectroscopy (XPS). The electrochemical determination of UO(2)(2+) was accomplished, after preconcentration under open circuit potential, by square wave voltammetry.