The rapid and uniform growth of hydrogenated silicon (Si:H) films is essential for the manufacturing of future semiconductor devices; therefore, Si:H films are mainly deposited using SiH4-based plasmas. An increase in the pressure of the mixture gas has been demonstrated to increase the deposition rate in the SiH4-based plasmas. The fact that SiH4 more efficiently generates Si2H6 at higher gas pressures requires a theoretical investigation of the reactivity of Si2H6 on various surfaces. Therefore, we conducted first-principles density functional theory (DFT) calculations to understand the surface reactivity of Si2H6 on both hydrogenated (H-covered) Si(001) and Si(111) surfaces. The reactivity of Si2H6 molecules on hydrogenated Si surfaces was more energetically favorable than on clean Si surfaces. We also found that the hydrogenated Si(111) surface is the most efficient surface because the dissociation of Si2H6 on the hydrogenated Si(111) surface are thermodynamically and kinetically more favorable than those on the hydrogenated Si(001) surface. Finally, we simulated the SiH4/He capacitively coupled plasma (CCP) discharges for Si:H films deposition.