A novel sandwich-like structured Co-Al LDH-Carbon Nanotube (CNT) composite has been successfully synthesized by the elegant combination between exfoliated Co-Al LDH nanosheets and modified CNTs, which was achieved through an electrostatic assembly method. It is worth noting that the negatively charged CNTs, sandwiched between the positively charged nanosheets via the electrostatic force, can not only expand the area of contact of electrolyte ions but also highly improve the conductivity. The as-prepared Co-Al LDHs-CNTs composite exhibited a high specific capacitance of 884 F g(-1) and a good cycle stability over 2000 cycles. Therefore, such a facile synthetic route to fabricate the layered structure composite may open a new strategy to prepare other composites with largely enhanced electrochemical properties, which can be of great promise in energy storage device application.