AbstractModification of material surfaces with polymers is an effective method to develop applicable polymer–material composites. Recently, multicomponent reactions (MCRs) have found their roles in advanced polymer chemistry and applied in surface modification. In this mini review, recent results of MCRs for surface modification are summarized, including the utilization of MCRs as coupling tools to link polymers on material surfaces, and polymers containing multicomponent structures for surface modification. The unique properties of these polymer–material composites stemming from MCRs are introduced, and the preliminary applications of these composites are also discussed.