© 2020 Elsevier B.V. Focusing on the treatment of pharmaceuticals contaminated water by advanced oxidation processes, a novel three dimensional silicate glass matrix (3-DG) coupled Cu2O/Cu2V2O7 p-n heterojunction was constructed by in-situ hydrothermal technique. The optimal Cu2O/Cu2V2O7 with 30 wt % Cu2V2O7 (CV-30) degrades 90.1 % sulfamethoxazole (SMX) in 60 min and nearly 100 % removal in 45 min via coupling with 3-DG. Under natural sunlight ∼ 80 % SMX removal was observed. The internal electric field of the p-n junction facilitates the electron flow via the interface. 3-D silicate glass increases the visible light absorption dramatically via internal reflection which facilitates higher exposure for the junction and shortens the diffusion length of charge carriers. The effect of reaction parameters suggests that HCO3− and CO32− ions substantially escalate the SMX removal rate. Scavenging experiments and ESR probe suggest [rad]O2− as the main active species followed by [rad]OH radicals. The degradation products were detected by LC–MS analysis and a degradation mechanism was also predicted. The photocatalytic mechanism was explained in terms of the electron transfer facilitated by conventional transfer and Z-scheme. This strategy to construct such highly visible and solar active p-n heterojunctions will pave way for future opportunities for the degradation of recalcitrant pharmaceutical pollutants.