Calculations of the polymerization rate and molecular weight development in the nitroxide‐mediated radical polymerization (NMRP) of styrene (STY), using hydroxyl‐TEMPO and dibenzoyl peroxide (BPO), and activated by microwave irradiation (MI), are presented. The calculations are based on a kinetic model developed in our group. Microwave activation is modeled by three approaches: microwave‐activated production of free radicals from monomer molecules, microwave‐enhanced thermal initiation, and microwave‐enhanced dormant polymer activation. The results obtained are compared against experimental data from the literature. The first approach is the most adequate. The NMRP of STY using TEMPO, BPO, and conductive heating, and the NMRP of STY activated by MI, without initiator, are also analyzed as reference cases.