A facile and clean strategy for synthesizing unimodal polymethacrylates with narrow dispersity (Đ < 1.10) is successfully developed by a near‐infrared (NIR) light‐emitting diode (LED) light (λmax = 740 nm)‐controlled in situ bromine–iodine transformation reversible‐deactivation radical polymerization system without the use of NIR dyes and expensive catalysts. In this system, alkyl iodide ethyl α‐iodophenylacetate (EIPA) initiator is generated in situ by the nucleophilic substitution reaction between an alkyl bromide compound ethyl α‐bromophenylacetate and sodium iodide (NaI). At the same time, excessive NaI is also acted as a highly active catalyst by forming halogen bonds with terminal iodine of the polymer chains in this system to make it capable of precisely synthesizing polymethacrylates with narrow dispersities (Đ = 1.03–1.10). In addition, the strong penetration ability of NIR LED light is illustrated by the successful polymerization even through 11 pieces of A4 paper.