A novel concept for capillary electrophoresis-mass spectrometry (CE-MS) studies of neutral analytes is presented. The experimental approach is based on the implementation of electrochemically assisted injection (EAI) which enables the generation of charged species from neutral analytes. In this way electrophoretic separations can be performed without the use of surfactants leading to an excellent compatibility with ESI-MS. Various ferrocene species have been used as model compounds to demonstrate the potential of the EAI-CE-MS technique.