This minireview is written in honor of Vladimir A. Shuvalov, a pioneer in the area of primary photochemistry of both oxygenic and anoxygenic photosyntheses (See a News Report: Allakhverdiev et al. 2014). In the present paper, we describe the current state of the formation of the primary and secondary ion-radical pairs within photosystems (PS) II and I in oxygenic organisms. Spectral-kinetic studies of primary events in PS II and PS I, upon excitation by ~20 fs laser pulses, are now available and reviewed here; for PS II, excitation was centered at 710 nm, and for PS I, it was at 720 nm. In PS I, conditions were chosen to maximally increase the relative contribution of the direct excitation of the reaction center (RC) in order to separate the kinetics of the primary steps of charge separation in the RC from that of the excitation energy transfer in the antenna. Our results suggest that the sequence of the primary electron transfer reactions is P680 → ChlD1 → PheD1 → QA (PS II) and P700 → A 0A/A 0B → A 1A/A 1B (PS I). However, alternate routes of charge separation in PS II, under different excitation conditions, are not ruled out.