This paper presents the results obtained from a novel multifunctional analysis platform established on the basis of wide-bore electrophoresis (WBE) and CE. The WBE-CE system integrated various analytical steps including separation, transfer, reaction, detection, and storage into a single system. During the WBE-CE process, a distinct three-electrode format was adopted to continuously separate and transfer samples between WBE and CE without the interruption of switching on-and-off the power suppliers. This continuous mode of operation also helped to eliminate the need for exactly timing the transfer of specific samples zone from WBE to CE and avoided the danger of missing specific samples. Samples representing mixtures of acids, bases, or proteins were analyzed on this system for evaluating its feasibility and applicability. The results indicated that the resolution achieved on this WBE-CE system was better than either the WBE or the CE alone. Further, samples transferred out of the WBE system could participate in online reaction, such as enzymatic reaction in the CE. Alternatively, samples from the WBE system could be transferred out and stored offline in a vial for post-transfer reaction. The results demonstrated that this WBE-CE system has the potential to be a multifunctional platform for a range of applications.