So far, a number of approaches to synthesize microgel networks have been followed, while only in few cases a detailed control of the network architecture has been possible. Here, the photoinduced [2 + 2] cycloaddition reaction of cinnamylidene acetic acid (CAA) moieties coupled to four-arm star shaped oligo (ethylene glycol) (OEG) precursors was explored for the creation of microgels with defined polymer network structures. Based on a rational solvent selection and precursor dispersion in glass-capillary microfluidics, microgels could be successfully prepared by the proposed synthesis approach. Model reactions confirmed a quantitative network formation. Therefore, compared to common radical polymerization for microgel crosslinking, CAA-dimerization may be an alternative approach particularly when well defined network structures are desired. (C) 2017 Elsevier B.V. All rights reserved.