The selectivity rules of sum frequency generation spectroscopy were exploited to determine propyl chain order during the time-dependent oscillatory adsorption of propyltrimethoxysilane (PTMS) and Langmuir-type growth of propyldimethylmethoxysilane (PDMMS). During the early stages of film growth, molecular packing density determines the extent of propyl chain defects within both films with high surface coverage resulting in a film with fewer defects. Following this, an ordered monolayer-like film stabilizes on the Al2O3 substrate for both silanes. Although this result is intuitive for the Langmuir-type growth of PDMMS, the stabilization of molecular ordering despite the continuing oscillation in PTMS surface coverage indicates the presence of a stable monolayer, while it is the oligomerized PTMS dendrimers which continue to desorb and readsorb to the substrate. We also reveal for the first time, the formation of a physisorbed bilayer during the self-assembly process of PTMS. The presence of this ordered, physisorbed bilayer on top of the covalently bound PTMS film plays a key role in the process of the molecular self-assembly mechanism and is proposed to enable further condensation of the covalently bound film.