A new recombinant CN material (R-CN) was prepared with g-C3N4 as precursor by hydrothermal method combined with thermal recombination method, which has 2D ultra-thin structure, nanoscale folds, graphite-like texture and some pores, and has richer N and O elements than g-C3N4. R-CN can reduce high temperature decomposition peak of ammonium perchlorate (AP) to 356.06 oC, and its promoting effect is obviously better than that of g-C3N4. Based on specific structural composition and physicochemical properties of R-CN, a novel R-CN@MWO composite with core-shell was designed, which was applied to catalytic decomposition of AP and pressure enlarging effect during combustion process of cyclotrimethylenetrinitramine (RDX)+nitrocellulose (NC). With the introduction of R-CN@MWO, decomposition peak temperature and activation energy of AP are reduced by 104.67oC and 59.24 kJ mol−1, and peak pressure and pressurization rate of RDX+NC constant volume combustion test are increased by 11.33 and 118.54 times, respectively. Moreover, the combustion rate of R-CN@MWO-AP/HTPB propellant is 3.23 times that of AP/HTPB propellant. To sum up, R-CN as a coating layer can significantly enhance catalytic activity of MgWO4 for thermal decomposition of energetic materials.