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Solvated electron (esol−) is highly reducing species and apt to initiate monomers via one‐electron transfer reaction. Herein, utilizing the esol− solution of Na/hexamethylphosphoramide, radical and anionic initiations are observed respectively, which heavily depend on Na concentrations. Interestingly, this initiation system, in states of lower Na concentrations, higher molar conductivities and less...