We present an effective hybrid integration of PDMS microfluidic devices and fused silica capillaries. These hybrid microfluidic Integrated PDMS and Silica Capillary (iPSC) modules exhibit a novel architecture and method for leakage free CE sample injection requiring only a single high voltage source. Use of the iPSC devices is based on a modular approach which allows the capillary to be reused over 1,000 times whilst replacing the fluidics below it for different experiments. Integrating fused silica capillaries with PDMS microfluidics allows the direct application of a wide variety of well established conventional CE protocols for complex analyte separations and ESI-MS coupling, allowing users to focus on the sample analysis rather than the development of new separation protocols. The iPSC fabrication method is simple (3 steps) and quick (7 min).