In this work, we present the sensitive and selective determination of the widely used insecticide nitenpyram (NIT), utilizing a newly developed dual detection concept (DDC) for capillary electrophoresis (CE). This DDC was realized by combining two complementary detection principles, namely amperometric detection (AD) and mass spectrometry (MS), using a commercially available flow splitter (CE-AD/MS). The novel DDC was implemented utilizing a newly developed, modular, and user-friendly CE system with a unique capillary positioning mechanism to improve the workflow. A detailed description of the CE device can be found in the Supporting Information.We investigated the analytical performance of the novel DDC (CE-AD/MS) in the context of NIT determination.The NIT LOD, obtained by AD, was up to a factor of 14 lower than in case of MS in the context of CE-AD/MS. The qualitative and quantitative determination of NIT in pharmaceutical samples is presented as a possible application for the novel DDC. Additionally, the oxidation process during AD was examined by hyphenation of electrochemistry to CE-MS. image