A Supported Liquid Phase Catalyst (SLPC) coating was successfully applied for the Mizoroki–Heck reaction in micro flow. Foremost, extended on stream operation was enabled and the on stream performance stability was verified. Stable catalytic activity was achieved during two consecutive runs totaling 50 h, after an initial stabilization period. Further support for the catalytic stability was provided by the fact that no leached Pd was detected in the product. Highest obtained conversion was 94% at 230 °C and a 26 min residence time. When conversion was plotted versus residence time, the reaction was shown to fit the predictions of the kinetic model. To optimize the performance of the flow system, reaction conditions and different ligands for the catalyst were initially investigated in batch, as well as various different substrates. Ethylene glycol was found to be most effective as the solvent film, while the use of water led to degradation of the silica support.