We have developed a new method for analyte preconcentration on a microfluidic device using a porous membrane fabricated via sol-gel chemistry. These porous membranes were fabricated within the channels of glass microfluidic devices exploiting laminar flow to bring an alcoholic sol-gel precursor (titanium isopropoxide in 2-propanol) into contact with an alcohol-water solution at a channel cross intersection. These two streams reacted at the fluidic interface to form a porous titania membrane. The thickness of the membrane could be altered by changing the [H2O]. Analyte concentration was accomplished by applying a voltage across the titania membrane. The level of analyte enrichment was monitored, and enrichment factors of above 4000 in 400 s were obtained for 2,7-dichlorofluorescein.