We demonstrate that the combination of high speed separations on chip with a fast mass spectrometer enables electrophoretic separations with full mass spectra registration within a second. This was accomplished by coupling a microfluidic glass chip with an integrated nanospray emitter to a fast time of flight mass spectrometer working at 100 Hz for data acquisition. Applying field strengths up to 5800 V cm(-1) we achieved separations of model analytes such as pharmaceuticals and peptides with subsequent acquisition of full mass spectra within one second or slightly more.