The electron transfer to self-assembled molecular monolayers carrying a ferrocene (Fc) center, grafted on a flat Si(100) surface, is a recent subject of experimental investigation. We report here the density functional theory (DFT) ab initio calculation of Fc-silicon hybrid redox potentials. The systems were modeled with a slab of H-terminated Si(100) 1 x 1 and 2 x 1 surfaces: geometries were optimized using the ONIOM method, and solute-solvent interactions were included through the polarizable continuum model (PCM) method. Two new routes for Si functionalization with ethyl- (EtFC) and ethynyl-Fc (EFC) differing only in the unsaturation degree of the anchoring arm have been successfully explored, and the redox potential of the resulting hybrids has been measured by cyclic voltammetry: 0.675 and 0.851 V versus NHE for the EtFC and EFC derivatives, respectively. These values, along with the previously measured potential (0.700 V) for the mono-unsaturated derivative, vinyl-Fc, allow the relation between the unsaturation degree and the adduct redox potential to be studied. The comparison among the measured and computed potentials allows one to discriminate between different adduct isomers for the saturated species and more importantly provides strong indications that the carbon-carbon unsaturation initially present in the molecular arm used for anchoring to the surface is preserved upon addition, in contrast with the commonly accepted reaction mechanism.