In this paper, we present an approach to perform electrochromatographic separations on poly(dimethylsiloxane) chips: a fused-silica capillary containing a stationary phase was introduced directly into the chip. This approach would offer great flexibility since capillary modification methods are well known, and thus, with this kind of chip, different microfluidic devices having various functions could be prepared. Electrophoretic separations were first achieved by integrating an empty capillary into the chip to evaluate the analytical performances of this system. They were compared to those obtained with a classical chip. Finally, an electrochromatographic separation involving a capillary containing a hexyl acrylate-based monolith was performed. These preliminary results show this approach to be promising.