The role of cations in excitation energy distribution between the two photosystems of photosynthesis is well established. This paper provides evidence, for the first time, for an important role of anions in the regulation of distribution of absorbed light energy between the two photosystems. Inorganic anions caused redistribution of energy more in favour of photosystem I, as judged from measurements of chlorophyll a fluorescence transients, rates of electron transport in low light and 77 K fluorescence emission spectra: the Fv/Fm ratio was decreased by inorganic anions even in the presence of DCMU, the PS II electron transport was decreased whereas PS I electron transport was increased and the F735 (77 K emission from PS I)/F685 (77 K emission from PS II) ratio was increased. Such changes were observed with inorganic anions having different valencies (Cl- , SO4(2-), PO4(3-)): the higher the valency of the inorganic anion, the more the energy transferred towards PS I. Change in the valency of the inorganic anions thus regulates distribution of absorbed light energy between the two photosystems. However, organic anions like acetate, succinate, and citrate caused no significant changes in the Fv/Fm ratio, and in rates of PS I and PS II electron transport, showing their ineffectiveness in regulating light energy distribution.