Multicomponent reactions are of substantial significance not only for organic synthesis but also for polymer synthesis due to their more bond-forming events per synthetic operation. Generally due to that there are two or more reactions in one multicomponent reaction system, synergistic catalysis, in which the two or more reactions are activated by two or more different catalysts at the same time, is very important for achieving high-efficiency transformations. However, achieving synergistic catalysis via using two or more different catalyst simultaneously is a great challenge. Here, we propose a new reactant-synergistically catalyzed multicomponent reaction, in which the units coming from the reactant can synergistically catalyze the two reactions at the same time. Moreover, this multicomponent reaction can be extended to multicomponent polymerization, which is a very promising method for the preparation of functional polymers with defined-sequence. (C) 2014 Elsevier Ltd. All rights reserved.