The method of pulse laser photoelectron injection from metal into electrolyte solutions (PIMES) has been used to study the bulk and electrode reactions of intermediates (SF5 and SF4) obtained by reduction of SF6 by solvated electron in aqueous and methanolic solutions. The experimental data for both solvents were explained in the framework of the general reaction mechanism. The total electron-transfer number v(0) of the photoelectrochemical process was found to depend on both the electrode potential phi and the delay time, increasing from 2 to 6. The SF5. radical undergoes one-electron reduction to SF4, which subsequently undergoes four-electron reduction to S. The rate constants of the homogeneous decay of the radical anion SF6-(greater than or equal to 10(10) s(-1)) and the reactions of the SF5. radical with water (3X10(4) M(-1) s(-1)) and methanol (less than or equal to 2x10(4) M(-1) s(-1)) have been estimated. The time-resolved photopolarograms allow the following stages in the electrode reactions of fast transients to be distinguished : SF5.+e(m)(-)-->SF4+F- (occurring at delay times t<100 ns for phi less than or equal to-0.2 V/SCE/); SF4+2e(m)(-)-->SF2+2F(-)(t less than or equal to 100-200 ns, half-wave potential phi(1/2) is -0.6 V for water and -1.2 V for methanol); SF2+2e(m)(-)-->S+2F(-) (at times up to 10 mu s depending on the electrode potential).