Sodium pentazolate （NaN₅） is a nitrogen-rich compound with high energy density and rapid energy release rate. However， its combustion suffers from slow burning rate， high sensitivity， and poor self-sustaining combustion. In this study， by using a coordination complex strategy based on NaN₅ with graphene oxide （GO） and polydopamine （PDA）， a series of NaN₅-based composite energetic materials were synthesized via solvent evaporation and co-precipitation. The morphology and structure of the composites were characterized by scanning electron microscopy （SEM）， Fourier-transform infrared spectroscopy （FT-IR）， and X-ray photoelectron spectroscopy （XPS）. The thermal decomposition behavior and mechanism were investigated using synchronous thermal analysis （TG-DSC） and reaction kinetics simulations. The combustion and detonation performances were evaluated via hot-wire ignition tests. Results demonstrate that after GO/PDA modification， the structure of NaN₅-3%GO-1%PDA is optimized from cubic crystal to porous folded layer with strong interfacial bonding. Compared with pristine NaN₅， the stepwise decomposition temperature difference of NaN₅-3%GO-1%PDA is reduced by 61.1 ℃， the activation energy decreases by 30.7 kJ·mol^-1， and the detonation growth time is reduced from 33.33 μs to 16.67 μs ， proving that NaN₅-3%GO-1%PDA has a faster energy release rate.