We are studying the effects of etch conditions on the surface morphology, chemistry, and luminescent properties of porous silicon (PS) films. Luminescent silicon films are produced by chemical etching using solutions of HNO3 in HF and by anodic etching using aqueous HF electrolytes. Films produced by both methods are analyzed and compared using photoluminescence (PL), vibrational, and X-ray photoelectron (XPS) spectroscopies. The initial characterization of PS is performed immediately following the etching process, resulting in oxide-free films (as confirmed by XPS). In chemically etched PS films, the luminescent intensity decreases as the vol. % HNO3 in etch solution increases. Spectral features evolve in the PL spectrum of chemically etched films as the result of aging under ambient conditions and when the films are cooled under illumination. Moreover, we have also found that increased electrolyte convection results in a decrease in photoluminescence intensity of PS films formed anodically. The role of electrolyte flow in modifying the luminescent properties of PS is being evaluated in an etch cell with well-characterized hydrodynamics.