A series of acrylic monomers based on cyclometalated iridium(III) complexes have been synthesized based on common phosphorescent emitters for organic light‐emitting diodes. A simple room‐temperature polymerization procedure for these materials was developed using Cu(0) reversible deactivation radical polymerization, providing polymers with low dispersities of 1.08–1.14 at conversions from 81 to 93% when the Ir complexes are copolymerized with a carbazole‐based acrylic host. These methods were also found to be suitable for the preparation of high‐molecular‐weight polymers with M
n approaching 40,000 Da, as well as block copolymers formed in one pot from the chain extension of methyl acrylate. This scalable room‐temperature synthesis of iridium‐containing copolymers and block copolymers provides a useful route to optoelectronic materials, which we anticipate can be readily adapted to a broad range of acrylic metallopolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2539–2546