Isotopic labeling and step coverage studies of silicon oxide deposited from tetraethoxysilane (TEOS) have been carried out by introducing TEOS(16O) downstream from an 18O2 discharge. Rutherford backscattering (RBS) data on films deposited near 440 °C show that, on average, one Si–O bond in the original TEOS molecule is preserved in the process, while mass spectrometric results indicate only H216O and C18O16O as gaseous products of the cleavage of the remaining three Si–O bonds. Infrared analyses of films deposited at room temperature show large amounts of Si–OH in a gel‐like material, and the presence of a CO species. The results suggest a mechanism dominated by diffusion and condensation of Si–OH species that form extensive chains and preserve an Si–16O bond from the original precursor. This is followed by cross‐linking to form the final silicate network; however, Si–O bond cleavage is apparently occurring at potential cross‐linking sites via a carbonate intermediate that promotes isotopic scrambling. Step coverage is shown to be better under conditions (high temperature, low TEOS flow) that favor a low concentration of surface precursors during film growth. This is consistent with the proposed mechanism since second‐order condensation reactions of surface species under these conditions would be kinetically limited allowing effective mean free paths to increase dramatically. Experimental parameters and techniques, such as modulated chemical feeds to enhance the role of surface migration also lead to improved step coverage. However, we also conclude that perfectly conformal coverage based on similar mechanisms will inevitably lead to void formation in high‐aspect‐ratio topography because of transport limita- - tions.