The emergence of neoteric synthetic routes for materials functionalization is an interesting phenomenon in materials chemistry. In particular, the union of materials chemistry with multicomponent reactions (MCRs) opens a new avenue leading to the realm of highly innovative functionalized architectures with unique features. MCRs have recently been recognized as considerable part of the synthetic chemist's toolbox due to their great efficiency, inherent molecular diversity, atom and pot economy along with operational simplicity. Also, MCRs can improve E-factor and mass intensity as important green chemistry metrics. By rational tuning of the materials, as well as the MCRs, wide ranges of functionalized materials can be produced with tailorable properties that can play important roles in the plethora of applications. To date, there has not reported any exclusive review of a materials functionalization with MCRs. This critical review highlights the state-of-the-art on the one-pot functionalization of carbonaceous and siliceous materials, polysaccharides, proteins, enzymes, synthetic polymers, etc., via diverse kind of MCRs like Ugi, Passerini, Petasis, Khabachnik-Fields, Biginelli, and MALI reactions through covalent or noncovalent manners. Besides the complementary discussion of synthetic routes, superior properties and detailed applicability of each functionalized material in modern technologies are discussed. Our outlook also emphasizes future strategies for this unprecedented area and their use as materials for industrial implementation. With no doubt, MCRs-functionalization of materials bridges the gap between materials science domain and applied chemistry.