We present a novel multi-emitter electrospray ionization (ESI) interface for the coupling of microfluidic free-flow electrophoresis (μFFE) with mass spectrometry (MS). The effluents of the μFFE outlets are analyzed in near real-time, allowing a direct optimization of the electrophoretic separation and an online monitoring of qualitative sample compositions. The short measurement time of just a few seconds for all outlets even enables a reasonable time-dependent monitoring. As a proof of concept, we employ the multi-emitter ESI interface for the continuous identification of analytes at 15 μFFE outlets via MS to optimize the μFFE separation of important players of cellular respiration in operando. The results indicate great potential of the presented system in downstream processing control, for example, for the monitoring and purification of products in continuous-flow microreactors.