Abstract The electrochemical reduction of uracil in dimethyl sulfoxide was investigated, using d.c.and a.c. polarography, cyclic voltammetry, and controlled potential electrolysis. Uracil is reduced in a one-electron step ( E 1/2=−2.3 V); the apparent number of electrons transferred ( n) decreases from one at infinite dilution to one-half at concentrations above 1m M. The concentration dependent n-value is due to proton transfer by the parent compound to the radical anion formed on reduction. Such a proton transfer, which has been observed for 2-hydroxypyrimidine, deactivates part of the uracil, which would otherwise be available for reduction, by formation of the more difficultly reducible conjugate base. The uracil anion forms insoluble mercury salts, producing two oxidation waves ( E 1/2 of −0.1 and −0.3 V); the latter wave is due to formation of a passivating film on the electrode. Digital simulations indicate that the protonation rate exceeds 10 5 M −1 s −1 and that, at low uracil concentration, some of the free radical formed on protonation is further reduced. At concentrations exceeding 1 m M, all of the free radical dimerizes. The effect of added acids and base on the electrochemical behavior is described.