Sol-gel synthesis of titania typically produces a mixture of brookite and anatase. Rietveld refinements were used to systematically track the brookite content and particle size as functions of synthetic variables. Results demonstrate that brookite content and anatase particle size decrease with decreasing Ti/H2O ratios. In syntheses at pH 3, the addition of HCl resulted in increased amorphous content compared to samples synthesized using HNO3. Similar amorphous contents were observed for particles prepared at pH 6-9. Hydrothermal aging for 4 h at 200°C of sol-gel products containing substantial amorphous titania resulted in higher brookite content than did hydrothermal aging of sol-gel products containing little to no amorphous titania. Finally, dialysis prior to hydrothermal aging appeared to inhibit phase transformation from brookite to anatase in aged materials. Results presented demonstrate that considerable control over the relative anatase and brookite contents can be achieved through control of synthetic variables.