Anodic decomposition of a vinylmagnesium halide or an ethynylmagnesium halide at a surface-hydrogenated silicon electrode leads to the formation of polymeric layers covalently anchored to the silicon surface. These layers have been characterized using spectroellipsometry and photoluminescence, infrared, and X-ray photoelectron spectroscopy. In the case of vinyl precursors, it appears that the multiple bonds are largely broken in the process. In the case of ethynyl, the layer formation rate is much higher for the chloride than for the bromide. The obtained polymer appears as a saturated skeleton bearing halide and unsaturated ethynyl groups. Furthermore, it appears that the solvent may be attacked by the ethynyl radicals leading to contamination of the polymer by solvent fragments, an effect that can largely be avoided by using appropriate solvents. The reaction pathways are discussed.