Kinetic investigations of the quaternization reactions of poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) with alkyl halides (1‐iodobutane, 1‐iodoheptane, and 1‐iododecane) are carried out at different temperatures. For this purpose, a PDMAEMA (M_n = 17.8 kDa, Ð = 1.35) synthesized via reversible addition fragmentation chain transfer polymerization is utilized. The progress of the quaternization reactions is followed by proton nuclear magnetic resonance. As expected, the rate of quaternization is higher with increasing temperature. The experimental data are used to determine the following kinetic parameters: order of the reaction, Arrhenius' pre‐exponential factor, and activation energy. To the best of knowledge, this is the first contribution that provides detailed kinetic data of the quaternization reactions on PDMAEMA.