In the past few decades, ceramic/polymer nanocomposites have been extensively studied due to their relatively large dielectric constant, high electric energy density, and large charge–discharge efficiency. Antiferroelectric (AFE) materials possess a low remnant polarization (P r) and relatively high saturation polarization (P s), which can induce higher storage energy density than relaxor ferroelectric materials. In this investigation, AgNbO3-based AFE ceramic nanoparticles were grafted with a layer of poly(methyl methacrylate) (PMMA) to form AgNbO3–g-PMMA nanoparticles and then the obtained nanoparticles were embedded into a poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) matrix to form an AgNbO3–g-PMMA/PVDF-HFP (AN–g-PMMA/HFP) nanocomposite film. After characterization, it was found that the dielectric constant of the AN–g-PMMA/HFP-5 (5% AgNbO3) nanocomposite film was 12.3, which was 43% higher than that of the pristine PVDF-HFP film. The AN–g-PMMA/HFP-5 nanocomposite film exhibited the largest breakdown field of 500 MV m−1 and the highest energy density of 13 J cm−3, which was increased by 32.5% (from 9.82 to 13 J cm−3), as compared with that of the pristine PVDF-HFP film. The AN–g-PMMA/HFP-5 film exhibited a charge–discharge efficiency of 69.5% at 500 MV m−1, which is 9.5% higher than that of the pristine PVDF-HFP film. This AgNbO3-based nanocomposite film shows great promise for AFE nanocomposite for high energy density capacitor applications.