Multifarious layered materials have received extensive concern in the field of energy storage due to their distinctive two-dimensional (2D) structure. However, the natural tendency to be re-superimposed and the inherent disadvantages of a single 2D material significantly limit their performance. In this work, the delaminated Ti3C2Tx (d-Ti3C2Tx)/cobalt-aluminum layered double hydroxide (Ti3C2Tx/CoAl-LDH) composites are prepared by layer-by-layer self-assembly driven by electrostatic interaction. The alternate Ti3C2Tx and CoAl-LDH layers prevent each other from restacking and the obtained Ti3C2Tx/CoAl-LDH heterostructure combine the advantages of high electron conductivity of Ti3C2Tx and high electrochemical activity of CoAl-LDH, thus effectively improving the electrochemical reactivity of electrode materials and accelerating the kinetics of Faraday reaction. As a consequence, as a cathode for alkaline hybrid battery, the Ti3C2Tx/CoAl-LDH electrode exhibits a high specific capacity of 106 mAh g−1 at a current density of 0.5 A g−1 and excellent rate capability (78% at 10 A g−1), with an excellent cycling stability of 90% retention after 5000 cycles at 4 A g−1. This work provides an alternative route to design advanced 2D electrode materials, thus exploiting their full potentials for alkaline hybrid batteries.