A series of new energetic polymers of poly(vinyl benzal acetal)-g-polyglycidylazides (PVB-g-GAPs) were prepared by the cross-linking reactions between poly(vinyl benzal acetal) (PVB) and four different molecular weight polyglycidylazides (GAPs), and their structures were characterized by ATR-FTIR, UV-Vis, 1 H NMR and 13 C NMR. The glass-transition temperatures of PVB-g-GAPs were evaluated by DSC method and the thermal stabilities of PVB-g-GAPs were tested by DTA and TGA methods. The results indicated that all PVB-g-GAPs exhibited good resistance to thermal decomposition up to 200°C and the thermal stability order of the four PVB-g-GAPs were PVB-g-2 # GAP (246°C) > PVB-g-3 # GAP (244°C) > PVB-g-4 # GAP (236°C) > PVBg-1 # GAP (231°C). The glass transition temperatures of PVBg-GAPs from DSC method suggested that the synthesized copolymers were thermoplastic elastomer. Moreover, the compatibilities of PVB-g-4 # GAP with the energetic components of TNT-based melt explosives (HMX, RDX, TNT and TATB) were studied by using the non-isothermal DSC method. The results indicated that PVB-g-4 # GAP exhibited good compatibility with TNT, TATB and HMX, and could be safely used in melt cast explosives.