Polydimethylsiloxane containing methacryloyloxy and methoxy silane groups (MAPDMS)-microcapsule-SiO₂ (MPMS) functional materials were prepared by constructing micro-nano hierarchical structures on the surface of MAPDMS matrix. Herein, MAPDMS@1,1-stilbene-modified hydrolyzed polyglycidyl methacrylate/graphene oxide/dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (MAPDMS@PGMA_m/GO/QC18) self-healing microcapsules with compact multi-shell structure were synthesized and combined with nano-SiO₂ to construct the hierarchical structures. Furthermore, ultraviolet (UV)/moisture dual curing mode was introduced into deep curing reaction and efficient self-healing reaction of the MPMS. The results show that the introduction of UV/moisture dual curing mode and micro-nano hierarchical structure gives MPMS functional materials excellent mechanical properties, antifouling properties, self-healing properties, and antibacterial properties. The shear strength and tensile strength of MPMS increase from 3.32 and 4.26 MPa of MAPDMS to 3.81 and 5.06 MPa, respectively. Its static contact angle increases from 115.9° of MAPDMS to 156.5°, and its slide angle decreases from 68.5° of MAPDMS to 7.8°, respectively. The antifouling performance of MPMS against seawater, soy sauce, juice, coffee, protein, and other contaminants is effectively improved compared with MAPDMS matrix. At the same time, the tensile strength and elongation at break of MPMS after healing reach 98.22% and 96.57% of those in original state, respectively. In addition, the antibacterial rates of MPMS against Escherichia coli and Staphylococcus aureus reach 99.85% and 100%, respectively. The MPMS prepared in this paper is expected to be widely used in marine antifouling, pipeline network, anti-icing, microfluidics, wearable devices, medical devices, electrochemical biosensors, and other fields.