1. In fresh chloroplasts,three b-type cytochromes exist. These are b-559HP (lambda max, 559 nm; Em at pH 7, +370 mV; pH-independent Em), b-559LP (lambda max, 559 nm; Em at pH 7, +20 mV; pH-independent Em) and b-563 (lambda max, 563 nm; Em at pH 7, -110 mV; pH-independent Em), b-559HP may be converted to a lower potential form (lambda max, 559 nm; Em at pH 7, +110 mV; pH-independent Em). 2. In catalytically active b-f particle preparations, three cytochromes exist. These are cytochrome f (lambda max, 554 nm; Em at pH 7, +375 mV, pK on oxidised cytochrome at pH 9), b-563 (lambda max, 563 nm; Em at pH 7, -90 mV, small pH-dependence of Em) and a b-559 species (lambda max, 559 nm, Em at pH 7, +85 mV; pH-independent Em). 3. A positive method of demonstration and estimation of b-559LP in fresh chloroplasts is described which involves the use of menadiol as a selective reductant of b-559LP.