Cyclohexa-1,3-dienes bearing a tetrafluoroethylene group underwent highly regioselective hydrosilylation in the presence of 1-10 mol % Co2(CO)8 in 1,2-dichloroethane under mild conditions (reflux, 3 h), which led to an abundant yield of homoallylsilanes. Mechanistic studies proved that the reaction proceeds as per the modified Chalk-Harrod mechanism; via DFT calculation, the reason for homoallylsilanes being exclusively obtained was demonstrated. The formal synthesis of a tetrafluorinated negative-type liquid crystal demonstrated the synthetic utility of such hydrosilylation.