Organic photoelectrochemical (PEC) cells for solar water splitting typically utilize bulk heterojunction (BHJ) structures to circumvent the intrinsically short exciton diffusion lengths of organic semiconductors. However, stochastic donor/acceptor networks in BHJs often result in disordered interfacial contacts, leading to severe charge recombination. Herein, we report a pseudo-bilayer (PS-Bi) organic photoanode featuring a vertically ordered donor–acceptor configuration established via sequential deposition. Our systematic investigation reveals that this PS-Bi structure promotes selective charge transport and suppresses recombination due to its high domain purity, thereby facilitating efficient charge transfer at the interface. Consequently, the optimized PS-Bi photoanodes deliver an enhanced average photocurrent density (Jph) of 1.75 ± 0.03 mA cm−2 at 1.23 V versus the reversible hydrogen electrode for solar water oxidation, while simultaneously exhibiting a significant cathodic onset shift and extended operational stability compared to the BHJ counterpart (Jph = 1.44 ± 0.07 mA cm−2). This study demonstrates that employing the PS-Bi structure is a promising strategy for achieving high-performance and stable organic PEC systems for sustainable solar fuel production.