A silicon-based microchip for electrochromatographic separations is presented. Apart from a microfluidic network, the microchip has integrated UV-transparent waveguides for detection and integrated couplers for optical fibers on the chip, yielding the most complete chromatography microchip to date in terms of the integration of optical components. The microfluidic network and the optical components are fabricated in a single etching step in silicon and subsequently thermally oxidized. The separation column consists of a regular array of microfabricated solid support structures with a monolayer of an octylsilane covalently bonded to the surfaces to provide chromatographic interaction. The chip features a 1 mm long U-shaped detection cell and planar silicon dioxide waveguides that couple light to and from the detection cell. Microfabricated on-chip fiber couplers assure perfect alignment of optical fibers to the waveguides. The entire oxidized silicon microchip structure is sealed with a glass lid. Reversed phase electrochromatographic separation of three neutral compounds is demonstrated using UV absorbance detection at 254 nm. Baseline separation of the analytes is achieved in less than two minutes.