Linear and branched polymers of 2-(dimethylamino)ethyl methacrylate (PDMAEMA) were synthesized in flow by atom transfer radical polymerization (ATRP) and self-condensing vinyl copolymerization adapted to ATRP, respectively, in capillary type stainless steel coiled tube (CT) microreactors. Coil flow inversion (CFI) was introduced to achieve better mixing and narrower residence time distributions during polymerization. This strategy was adopted to improve control over macromolecular characteristics and polymer architecture. Polydispersity index (PDI), as an overall indicator of control over polymerization, was significantly lower for CFI in the case of linear PDMAEMA, 1.39 compared to 1.53 for CT. For branched polymers containing up to 10 mol % of inimer, a reduced PDI was also obtained for CFI microreactor. As for the branching efficiency, it was found to follow the following trend CFI > CT > batch reactor.