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Abstract Traditional mechanochemically controlled reversible‐deactivation radical polymerization (RDRP) utilizes ultrasound or ball milling to regenerate activators, which induce side reactions because of the high‐energy and high‐frequency stimuli. Here, we propose a facile approach for tribochemically controlled atom transfer radical polymerization (tribo‐ATRP) that relies on contact‐electro‐catalysis (CEC) between titanium oxide (TiO₂) particles and CuBr₂/tris(2‐pyridylmethylamine (TPMA), without any high‐energy input. Under the friction induced by stirring, the TiO₂particles are electrified, continuously reducing CuBr₂/TPMA into CuBr/TPMA, thereby conversing alkyl halides into active radicals to start ATRP. In addition, the effect of friction on the reaction was elucidated by theoretical simulation. The results indicated that increasing the frequency could reduce the energy barrier for the electron transfer from TiO₂particles to CuBr₂/TPMA. In this study, the design of tribo‐ATRP was successfully achieved, enabling CEC (ca. 10 Hz) access to a variety of polymers with predetermined molecular weights, low dispersity, and high chain‐end fidelity.