A rapid and sensitive linear sweep polarographic method for the determination of progesterone is described. In basic media (0.01 M borax, pH 9), progesterone can be reduced at a dropping mercury electrode and the peak current increases greatly when low concentrations of cationic surfactants such as cetyltrimethylammonium bromide (CTAB) are added to the sample solution. Because of synergistic adsorption of progesterone and CTAB on the electrode surface, the polarographic wave exhibits a sensitivity that is 40 times greater than that in the absence of CTAB. A low detection limit of 2 x 10(-8) M is obtained. A linear relationship between peak current and concentration of progesterone holds in the range 8 x 10(-6)-4 x 10(-8) M. The electrochemical behaviour of progesterone was investigated, and an adsorptive reduction wave was confirmed. The method was developed for the assay of progesterone in pharmaceutical preparations and in the blood of pregnant women.