Abstract Multiphase chemical microreactors require a detailed knowledge of the flow conditions inside the reaction system. This paper reports flow visualization measurements of the two-phase gas–liquid flow pattern and the liquid velocity distribution inside liquid plugs of an intermittent flow. Rectangular cross-section silicon microchannels with hydraulic diameters between 187.5 and 218 μm are fabricated. Laser Induced Fluorescence (LIF) is used to determine the flow pattern. To analyze the influence of the liquid properties and the channel diameter on the two-phase flow pattern, we present flow regime maps using different channel geometries and fluids. A universal flow pattern map based on dimensional analysis is presented. In contrast to microchannel flows, a great number of correlations for flow characteristics for multiphase flow in (round) pipes with diameters >1 mm exist. We compare our experimental results from optical flow visualizations in microreactors with common flow correlations and regime maps for macro- and microchannels. The recirculation motion in the liquid segments of an intermittent gas–liquid flow is analyzed using micron-resolution particle image velocimetry (μPIV). The velocity distribution influences the mixing and the mass transport towards the reactive phase interface dealing with two-phase chemical reactions. For straight microchannels hardly any mass transport over the center line is quantified. For enhanced mixing geometrical adaptations are suggested.