Si quantum dots (QDs) capped with π-conjugated molecules (1-octene, phenylacetylene, and 1, 4-diethynylbenzene) exhibit red-shift in ultraviolet-visible absorption and photoluminescence spectroscopy. In order to pioneer the electron transport properties of silicon (Si) quantum dot hybrid polymers, we investigated the electron transport properties of benzene molecule in silicon electrodes, based on nonequilibrium Green's function (NEGF) method. Colloidal 4-ethynylstyryl and octyl co-capping silicon quantum dot (4-Es/Oct Si QD) was synthesized and its spin-coated films were fabricated at three different curing temperatures, 150, 250, and 350 °C. The increase in their electrical conductivities is due to strong electronic coupling between adjacent QDs in the Si QD solids, inducing significant changes in the valence band photoemission feature and optical properties. The quantum-chemical calculations of the electronic coupling in π-conjugated molecule-bridged Si QD dimer were performed to investigate non-adiabatic electron transfer between the adjacent QDs in the QD solid. Si QD clusters were synthesized by Sonogashira C˗C coupling reaction between 4˗Es/Oct Si QD and 2,5˗dibromo˗3˗hexylthiophene. The Si QD clusters showed significant red-shift, indicating the strengthening of the electronic coupling after C˗C cross˗coupling reaction.