The rates of electron flow catalyzed by a variety of unsubstituted and C- or N-methylated quinonediimine electron acceptors in a reaction requiring photosystem II in KCN-inhibited chloroplasts vary according to the structure of acceptor used. Quinonediimine, but not quinone, electron acceptor activities are inhibited by a variety of uncouplers. Kinetic analysis of this inhibition shows that it is competitive. Low concentrations of aniline also inhibit the activity of C-methylated quinonediimines, but this appears to be due to a chemical reaction between the acceptor and aniline at low pH inside the chloroplast. Light-induced uptake of a quinonediimine, p-phenylenediimine, was shown to occur in a DCMU-sensitive reaction. Methylamine uncoupling inhibits this uptake to the same extent as it inhibits electron flow. Experiments with a lipophobic acceptor, N,N,N',N'-tetramethyl-p-phenylenediimine, indicate that it catalyzes electron flow by the same mechanism as other quinonediimines. A model is proposed to account for quinonediimine-catalyzed electron flow.