Capillary electrophoresis coupled with contactless conductivity detector was applied to characterize BGE/segment/segment/BGE and BGE/segment/electrolyte/segment/BGE systems, where segment is the phase of mixed micelles migrating surrounded by BGE and composition of the first segment≠second segment. It was established that both systems are subject of evolution during electrophoretic run induced by different electrophoretic mobilities of segments and the phenomenon that generates the evolution is exchange of micelles between the two segments. This leads to segments re-equilibration during a run, which generates sub-zones from the two segments in the form of a cumulative zone or two isolated zones, depending on the injection scheme applied. Further analysis based on the system BGE/segment/electrolyte/segment/BGE shows that electrolyte solution between segments can act as a spacer to isolate the two micellar segments, and thereby to control the exchange of micelles between the two segments. Established features for both systems were further implemented towards characterization of the transport of nanocrystals (NCs) between two segments using CE/UV-vis technique and two examples were discussed: (i) on-line coating of NCs with surfactants and (ii) distribution of NCs between segments. The former aspect was found to be useful to discuss the state of particle in micellar media, whereas the latter shows system ability for the transport of NCs from the first segment or BGE based sample to the second segment, controlled by the electrolyte characteristics. It was concluded that transport of micelles and NCs is the subject of the same phenomena since basic electrolyte characteristics, i.e. length and concentration, act in the same way. This means that NCs in these systems can play the role of pseudomicelles, which mimic behaviour of micelles. Definitely, the tools established in the present work can be used to examine dynamic phenomena for pseudophase during electrophoresis and for NCs migrating in the presence of pseudophase in various configurations.