The shape of the molecular weight distribution (MWD) has great influence over the end-use properties of the polymer resin. Reported techniques for the production of polymer resins with bimodal MWI)s are based on the manipulation of certain operating conditions, such as the chain-transfer-agent concentration, among others. Living free-radical polymerization can be successfully used to achieve control over the molecular weight and architecture of the polymer resin and produce living polymer chains. Among the available techniques, the nitroxide-mediated system is one of the most commonly used. The key feature is that the nitroxide, for example, 2,2,6,6-tetramethylpiperdinyl-l-oxy (TEMPO), reversibly deactivates the growing radical, which provides for the controlled growth of the polymer chain. In this work, we present a study involving the sequential use of nitroxide-mediated and conventional free-radical techniques, aimed at the production of bimodal molecular weight distribution polymer resins, using a miniemulsion or a suspension polymerization system. No separation/purification technique is required between the polymerization steps. It is shown that bimodal MWD polymer resins of styrene and butyl acrylate can be successfully produced with the proposed technique. Independent control of the height and position of the peaks (i.e., relative proportion and molecular weight) of the distribution was achieved by manipulating the duration of the nitroxide-mediated process and the initiator concentration of the conventional free-radical process, respectively. The low-molecular-weight peaks ranged from 2000 to 30 000 Da, while the high-molecular-weight peak ranged from 300 000 to 1200 000 Da in miniemulsion polymerizations and from 30 000 to 150 000 Da in suspension polymerization. Trimodal MWD polymer resins can also be produced in miniemulsion with the proposed polymerization technique if the concentration of chain-transfer agents is properly manipulated.