SiO2-based xerogels are highly porous materials that may enhance the performance of microelectronic devices due to their extremely low dielectric constants (epsilon=1.36-2.2). Conventional xerogel and aerogel manufacturing techniques include an expensive and hazardous supercritical drying step to deposit crack free, high porosity films. Ambient drying techniques have recently been developed and in this article, we discuss how the process parameters in the ambient drying process affect the properties of a spin-coated film. Successful spin-on deposition of highly porous (>70%), thick (>1 mu m), crack-free, xerogel films was accomplished using a solvent saturated atmosphere during spinning and aging. The saturated atmosphere allowed for the isolation of each processing step and a better understanding of the effects of process variable changes. The film porosity was controlled by varying the extent of silylation (surface modification), the aging time, or the initial water/silane ratio. Fourier transform infrared spectra demonstrated that silylation of xerogel films helps eliminate bound moisture in these films and renders them hydrophobic. Finally, the dielectric constants extrapolated from refractive index measurements were in good agreement with those obtained from our conventional electrical measurements.