The increased level of interest in the miniaturization of analytical devices has led to a focus on exploring new and inexpensive materials. This dissertation aims to investigate the combination of nascent textile-based microfluidics with electrophoretic control principles to develop the new groundbreaking textile-based electrofluidic systems for the direct and rapid characterization of analytes separated from complex mixtures and matrices. Capillary electrophoretic systems typically comprise inaccessible and fully enclosed micro-capillary or microchannels, with limited sample loading capacities and no direct access to the solutes within. Herein, we investigate the use of textile constructs as electrophoretic substrates to provide an open and surface-accessible separation platform. The techniques commonly utilized in capillary electrophoresis, including electrophoretic separation, isotachophoretic (ITP) preconcentration, and surface functionalization, were investigated using textile sub