The Barbier reaction, a widely utilized reaction for carbon–carbon bond formation, has played important roles in modern organic chemistry for more than a century. Here, we show its successful introduction to polymer chemistry. Through one-pot Barbier polyaddition (both A₂+B₂ type and AB type) of monomers containing an organic halide and a benzoyl group, a series of phenylmethanol group containing polymers, including polymonophenylmethanol (PMPM), polydiphenylmethanol (PDPM), and polytriphenylmethanol (PTPM), have been synthesized. Para-PTPM exhibits interesting aggregation-induced emission, tunable thermo-responsive over a wide temperature range, sensory, luminescence enhancement of fluorescent dye in solid-state and processing properties. This significantly expands the libraries of monomer and polymer, and opens up an avenue for the design and application of functional polymer materials.