We report the electrochemical investigation of 5% Al doped MoS2@rGO composite as a high-performance anode for sodium (Na)-ion batteries. The x-ray diffraction (XRD), Raman spectroscopy and high-resolution transmission electron microscopy characterizations reveal that the Al doping increase the interlayer spacing of (002) plane of MoS2 nanosheets and form a stable 1T phase. The galvanostatic charge–discharge measurements show the specific capacity stable around 450, 400, 350, 300 and 200 mAhg−1 at current densities of 0.05, 0.1, 0.3, 0.5 and 1 Ag−1, respectively. Also, we observe the capacity retentions of 86% and 66% at 0.1 and 0.3 Ag−1, respectively, over 200 cycles with a consistent Coulombic efficiency of nearly 100%. The cyclic voltammetry, galvanostatic intermittent titration technique, and electrochemical impedance spectroscopy are used to find the kinetic behavior and the obtained value of diffusion coefficient falls in the range of 10−10 to 10−12 cm2s−1. Intriguingly, the in-situ EIS also explains the electrochemical kinetics of the electrode at different charge–discharge states with the variation of charge transfer resistance. Moreover, the post cycling investigation using ex-situ XRD and photoemission spectroscopy indicate the coexistence of 1T/2H phase and field-emission scanning electron microscopy confirm the stable morphology after 500 cycles. Also, the Na-ion transport properties are calculated for 1T Al–MoS2@rGO interface and Al–MoS2–MoS2 interlayer host structure by theoretical calculations using density functional theory.