polymer bearing dual functions of macroinitiator and stabilizer, PISA can be realized by simultaneous polymerization and self-assembly procedures. [7][8][9] In a typical PISA procedure, the core-forming block is gradually extended and becomes insoluble with the conversion of monomer, and the formed block copolymer tends to be aggregated as various morphologies, such as spheres, worms, lamellae, vesicles, and so on. [10,11] Superior to the traditional postpolymerization self-assembly technique performed with highly diluted concentration (<1% w/w) and complicated operation procedures, the PISA technique features higher solid content (up to 50%) and simpler operation procedure. [5,6] The PISA technique has essentially accelerated the theoretical study and practical applications of self-assembled nanoparticles, and thus, is attracting more and more attention from researchers.On the one hand, most of the current PISA works are still based on the reversible addition-fragmentation chain transfer (RAFT) polymerization mechanism. [12][13][14][15][16][17][18][19][20][21][22][23][24] Relatively, nitroxide mediated polymerization (NMP), [25][26][27][28] atom transfer radical polymerization (ATRP), [29][30][31] living anionic polymerization, [32] and ring-opening metathesis polymerization (ROMP) [33] mechanisms are rarely involved in the PISA system. The reason can be attributed to some unavoidable drawbacks of each polymerization mechanism. For example, due to the intrinsic color question brought by copper catalyst, the normal ATRP PISA was originally attempted and later stagnated. [29][30][31]34,35] Fortunately, with the continuous optimization and improvement of the ATRP mechanism, the ATRP PISA was revived and greatly developed in recent years. For example, in our previous work, [36] the ppm copper catalyst system of initiators for continuous activator regeneration (ICAR) ATRP was successfully introduced into PISA using poly[oligo(ethylene oxide) methyl ether methacrylate] (POEOMA) (labeled as POEOMA 50 , 50 representing the degree of polymerization [DP]) as macroinitiator/stabilizer, poly(benzyl methacrylate) (PBnMA) as core-forming block, and ethanol as solvent. This work confirms the practical feasibility of ATRP PISA and presents an alternative way to enrich the PISA system. [37][38][39][40][41][42] On the other hand, most of the current RAFT PISA works are still focused on the morphology diagram by modulating Polymerization-Induced Self-Assembly The poly[oligo(ethylene oxide) methyl ether methacrylate]s, POEOMA 24 and POEOMA 78 with average degree of polymerization (DP) of 24 and 78, respectively, are separately achieved by initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP) of OEOMA 300 monomer. The mixtures of [POEOMA 24 ] 0 /[POEOMA 78 ] 0 = 1/1, 2/1, or 4/1 are employed as macroinitiator/stabilizer to practice the ICAR ATRP polymerization-induced self-assembly (PISA) of benzyl methacrylate (BnMA) at 65 °C. When the obtained dispersions are sequentially cooled to roo...