Dual detection concepts (DDCs) are becoming more and more popular in analytical chemistry. In this work, we describe a novel DDC for capillary electrophoresis (CE) consisting of an amperometric detector (AD) and a mass spectrometer (MS). This detector combination has a good complementarity as the AD exhibits high sensitivity, whereas the MS provides excellent selectivity. Both detectors are based on a destructive detection principle, making a serial detector arrangement impossible. Thus, for the realization of the DDC, the CE flow was divided into two parts with a flow splitter. The DDC was characterized in a proof-of-concept study with ferrocene derivates and a nonaqueous background electrolyte. We could show that splitting the CE flow was a suitable method for the instrumental realization of the DDC consisting of two destructive detectors. By lowering the height of the AD compared to the MS, it was possible to synchronize the detector responses. Additionally, for the chosen model system, we confirmed that the AD was much more reproducible and had lower limits of detection (LODs) than the MS. The LODs were identical for the DDC and the single-detection arrangements, indicating no sensitivity decrease due to the CE flow splitting. The DDC was successfully applied to determine the drug and doping agent trimetazidine.