Glucose intercalated NiMn layered double hydroxide (LDH) is successfully fabricated with a facile one-pot hydrothermal method, which expands interlayer distances to enhance cycling stability and break the bottleneck of Ni-based hydroxide in applications. Electrochemical measurements show that the annealing-treated glucose intercalated NiMn LDH (LDH-GA) delivers a high specific capacity of 1464Fg−1 at a current density of 0.5Ag−1 (852Fg−1 for pristine NiMn LDH). The enhanced performance is contributed to the small sized architectures, lower charge transfer resistance and faster reversible redox reactions. Through enlarging interlayer distance and robustly stabilizing LDH, the cycling stability is dramatically enhanced from 45% to 90% for over 1000 cycles. To further disclose the reason of the enhanced electrochemical performance of NiMn LDH, a molecular dynamics (MD) simulation is implemented to calculate the diffusion of the electrolyte ions, the ionic diffusion coefficient and the ionic conductivity inside the NiMn LDH nanopores for different interlayer distances. Based on the experimental and theoretical results, it suggests that the intercalation of glucose in NiMn LDH could be an effective approach to enhance electrochemical performance, of which it also could be generalized to intercalation of other molecules to stabilize the α-phase of LDH.