Herein, an innovative solution was proposed by engineering the pore-confinement microenvironment in hollow nanoporous carbon to enhance the enrichment and diffusion kinetics of reactants for an efficient peroxydisulfate-based electron transfer process (PDS-ETP). Specifically, hollow N-rich carbon plate-assembled flowers (NCU900) with accessible surface area and abundant nano-confined channels (< 4 nm) were synthesized via a secondary N doping strategy to activate PDS. The confined system (0.42 min−1) exhibits a 21-fold higher catalytic degradation kinetics than the unconfined system (0.02 min−1) toward bisphenol A, along with an outstanding stability (45 h, 94.59 %) evaluated by the continuous flow reactor. Density functional theory calculations show that the kinetics enhancement is attributed to the stronger PDS adsorption and electron transfer at active sites caused by sufficient confined space. This work aims to promote the rational design of carbon-based catalysts with a confinement effect for high-performance PDS-ETP.