Abstract: The crystalline red phosphorus nanoribbons (cRP NRs) are a new type of material with banded structure, which gives the crystalline red phosphorus nanoribbons unique physical and chemical properties, and makes it have a wide application prospect in the field of photocatalysis. However, the application of cRP NRs in photocatalysis is affected by the problems such as the fast recombination of photogenerated electron holes and the single type of free radicals. In order to improve the photocatalytic degradation efficiency of cRP NRs, the iron-based MOF material MIL-101-NH₂ has the advantages of high specific surface area and porosity, and the material was modified by constructing heterojunction. In this paper, we have successfully synthesized cRP NRs with MIL-101-NH₂ organic framework materials by solvothermal method. Subsequently, the composite was characterized by SEM and TEM, and the successful composite of cRP NRs and MIL-101-NH₂ was confirmed by element distribution scanning and XRD characteristic peaks. In the comparative experiment of photocatalytic degradation of tetracycline, cRP NRs/MIL-101-NH₂ showed excellent degradation efficiency, degrading about 80% after 90 min of light. Then, XPS spectral analysis, band gap measurement, Mott-Schottky curve determination and free radical trapping experiments were carried out, and it was confirmed that cRP NRs/MIL-101-NH₂ formed Z-scheme heterojunction.