Microplastics (MPs) in the water system could easily enter the human body and pose a potential threat, so finding a green and effective solution remains a great challenge. At present, the advanced oxidation technology represented by photocatalysis has been proven to be effective in the removal of organic pollutants, making it a feasible method to solve the problem of MP pollution. In this study, the photocatalytic degradation of typical MP polystyrene (PS) and polyethylene (PE) by a new quaternary layered double hydroxide composite photomaterial CuMgAlTi-R400 was tested under visible light irradiation. After 300 h of visible light irradiation, the average particle size of PS decreased by 54.2% compared with the initial average particle size. The smaller the particle size, the higher the degradation efficiency. The degradation pathway and mechanism of MPs were also studied by GC–MS, which showed that PS and PE produced hydroxyl and carbonyl intermediates in the process of photodegradation. This study demonstrated a green, economical, and effective strategy for the control of MPs in water.