The deposition of lithium in dimethylformamide (DMF) has been studied by means of galvanostatic measurements. The overpotential was recorded during constant current pulses of so short a duration that only a few monolayers per pulse were deposited. The experiments were carried out under conditions of minimum contamination of the metal surface. The deposition process of Li in DMF is irreversible, the electron transfer being the rate-determining step. A mechanism of Li electrodeposition in DMF was proposed.