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Abstract A facile and efficient two‐step synthesis ofp‐substituted tris(2‐pyridylmethyl)amine (TPMA) ligands to form Cu complexes with the highest activity to date in atom transfer radical polymerization (ATRP) is presented. In the divergent synthesis,p‐Cl substituents in tris(4‐chloro‐2‐pyridylmethyl)amine (TPMA^3Cl) were replaced in one step and high yield by electron‐donating cyclic amines (pyrrolidine (TPMA^PYR), piperidine (TPMA^PIP), and morpholine (TPMA^MOR)) by nucleophilic aromatic substitution. The [Cu^II(TPMA^NR2)Br]⁺complexes exhibited larger energy gaps between frontier molecular orbitals and >0.2 V more negative reduction potentials than [Cu^II(TPMA)Br]⁺, indicating >3 orders of magnitude higher ATRP activity. [Cu^I(TPMA^PYR)]⁺exhibited the highest reported activity for Br‐capped acrylate chain ends in DMF, and moderate activity toward C−F bonds at room temperature. ATRP ofn‐butyl acrylate using only 10–25 part per million loadings of [Cu^II(TPMA^NR2)Br]⁺exhibited excellent control.