We study microreactors with internal fields of posts as typical examples of structured microreactors to elucidate flow fields and their implications for mass transfer. Laser-induced fluorescence (LIF) visualization combined with image analysis is used to systematically quantify key features such as interfacial area, phase holdup and the characteristics of the post-wetting layer. The subsequent mass transport analysis yields insight into how the posts contribute to the overall enhanced mass transfer performance compared to open channels, and provides predictions of mass transfer performance under varying operating conditions. Computational fluid dynamic (CFD) simulations of multiphase flow using the volume-of-fluid (VOF) method are in good agreement with experimentally observed multiphase flows.