For nearly a century, the excessive discharge of organic contaminants has gradually polluted water and endangered people's health, and photocatalysis has been prominently employed to remove persistent recalcitrant organic. Here, MIL-101(Cr) was firstly employed to introduce thin-layered Bi2O2CO3 for the formation of Bi2O2CO3/MIL-101(Cr) nanosheet composite, by a simple and low-temperature in-situ growth approach. The phase, morphology, optical, and surface characteristics of the fabricated composite were characterized through XRD, FTIR, SEM-EDS, N-2 adsorption-desorption, UV-Vis DRS, PL, TG, and XPS techniques, and the ability in the photocatalytic breakdown of rhodamine B (RhB) molecule under visible light was also studied. The results of characterization analysis and optical analysis exhibited that Bi2O2CO3/MIL-101(Cr) has large pore size, good visible light response-ability, and the heterojunction created by intercalating Bi2O2CO3 on MIL-101(Cr). Photocatalytic studies revealed that Bi2O2CO3/MIL-101(Cr) had superior RhB degradation activity than pure MIL-101(Cr) and Bi2O2CO3, which achieved 97.1% with visible light irradiation for 20 mg/l RhB. Meanwhile, the Bi2O2CO3/MIL-101(Cr) composite displayed good recyclability after three cycles as revealed by XRD and FTIR analysis proving their excellent stability. This study provides feasible insight into developing novel and efficient MIL-101-based heterojunction catalysts for environmental remediation in the future.