Liquid chromatography combined with electrospray ionization is widely used for direct analysis of polar and labile molecules by mass spectrometry (LCMS). The online coupling in LCMS is a major strength but also causes a principal limitation – that each eluting analyte has to be analyzed immediately and is not available for detailed interrogation after the LCMS run. Here we develop a new chromatographic strategy, which removes this limitation. After column separation the flow is split, one portion is analyzed directly and the other is diverted to a capture capillary. After the direct LCMS run, the flow is switched and the portion stored in the capillary is analyzed (‘replay run’). We describe a set up consisting of an analytical column, a splitting valve and a focusing column, which performs at full sensitivity and undiminished chromatographic resolution. We demonstrate three principal advantages of this system; nearly continuous MS utilization, duplicate analysis without requirement for additional sample and targeting of important but under-sampled features in the replay run.