The effects of reversible manganese extraction on NADP + photoreduction were studied with higher plant subchloroplast preparations of photosystem II (PS II). Under anaerobic conditions, when the reaction centers (RCs) of PS II are “closed” (i.e. in the state [P680 Pheo] QA), and in the presence of ferredoxin-ferredoxin-NADP + reductase, NADP + reduction is observed at a rate of 0.8 -1.1 nmol/mg × chlorophyll × h. After complete removal of manganese from PS II, the rate of NADP + reduction is reduced 40 - 50-fold. Upon the addition of Mn at a concentration of approx. 4 Mn atoms per reaction center, the NADP + reduction is restored up to 85 -90% of the initial value. When half of this amount of Mn is combined with about 40 times of the equivalent concentration of other divalent ions (Ca 2+ , Sr 2+ , Mg 2+ etc.) the reaction is also reactivated. Dinoseb (10 -6 m) an inhibitor of electron transfer in PS II prevents NADP + photoreduction. It is concluded that under conditions when the first quinone acceptor, QA, is in its reduced state (Q A - ) electrons are transferred from reduced pheophytin (Pheo·̅) to NADP + , indicating that PS II can reduce NADP + without the participation of PS I. On the basis of these and literature data, an alternate pathway for electron phototransfer in PS II reaction centers of higher plants is suggested. Some problems concerning the Z-scheme are discussed.