A one-pot method is introduced for the successful synthesis of narrow-distributed (D = 1.22) vinyl polymer with both ultrahigh molecular weight (UHMW) (M-w = 1.31 x 10(6) g mol(-1)) and micro-/nanomorphology under mild conditions. The method involves the following four stages: homogeneous polymerization, polymerization-induced self-assembly (PISA), PISA and reorganization, and PISA and multiple reorganizations. The key points to the production of UHMW polystyrene are to minimize radical termination by segregating radicals in different nanoreactors and to ensure sufficient chain propagation by promoting further reorganizations of these reactors in situ. This method therefore endows polymeric materials with the outstanding properties of both UHMW and tunable micro-/nanoparticles under mild conditions in one pot.