The rapid recombination of electron-hole pairs and limited substrates are the most critical factors astricting the effect of catalytic therapy. Thus, two-dimensional interplanar heterojunction (BiOCl/Bi2O3) that prolongs the lifetime of excited electrons and holes and extends the selectivity of substrates under ultrasound irradiation is prepared to facilitate high-performance cancer therapy. An edge modification displacing marginal BiOCl to Bi2O3 is proposed to construct the interplanar heterojunction, promoting ultrathin nanosheets exfoliation due to the enhanced edge affinity with H2O. The spontaneously aligning Fermi levels mediate a built-in electric field-guided Z-scheme interplanar heterojunction, retard electron-hole pairs recombination, and improve redox potentials. Hence, these high-powered electrons and holes are capable of catalyzing diverse and stable substrates, such as the reduction reactions, O2 → ·O2- and CO2 → CO, and oxidation reactions, GSH → GSSG and H2O → ·OH. The Z-scheme interplanar heterojunction with the extending substrates selectivity completely breaks the tumor microenvironment limitation, exhibiting high anticancer activity.