We report the utility of controlled spacing of molecular monolayers on Si(111) surfaces by the use of sterically bulky silanes. The steric bulk of a 3,5-diphenolic linker of type Ph-diO-SiR3 (R = hexyl, phenyl, iPr)-as well as the smaller Ph-diOMe-is shown to control the surface coverage on Si(111). The para substituent was also changed from -F (small) to -OTf (triflate, large) to modulate the conformation of a selected bulky silane (SiR3; R = hexyl) to further control the steric environment of the monolayer. The surface coverage values are found to vary systematically from 57 → 21 → 15 → 11% for the series CH3 → hexyl → iPr → phenyl. Substitution at the para position (F → OTf) decreased the packing density for R = hexyl to as low as 8% (from 21%). The molecular coverage was also found to control the rate and extent of surface oxidation when unfunctionalized sites were allowed to oxidize. Following attachment, facile deprotection of the silanes was achieved by treatment with BBr3 to afford the diphenolic -OH groups. To electronically characterize the monolayers, voltammetry was performed in contact with liquid Hg to determine the barrier height, which was decreased by 70 mV as the coverage is increased. This study provides a synthetic rationale for controlling the packing density of surface linkers using electroless chemistry at semiconductor interfaces, thus providing further tunability and functionality of photoelectrochemical devices.