A detailled study of the impact of stereoelectronic effects of olefins in the Matsuda‐Heck‐reaction was addressed by kinetic studies. In addition to the stereoelectronic effects of the olefins used, their influence on the formation of the catalytic Pd colloids was also investigated. Depending on the olefin used, different particle size distributions were obtained on the one hand and, on the other hand, inhibition effects due to adsorption of the olefins on the Pd colloids were observed. Based on these findings, it was possible to optimize reaction conditions for the respective olefins. The presented kinetic data were supplemented by STEM‐measurements.