Polymer-based dielectric materials have been used in film capacitors due to their rapid charge-discharge rate, lightness, and low cost. Nevertheless, the energy storage properties of these dielectric films were limited by their weak polarization ability and low discharge energy density. Herein, the solution casting method was used to prepare all-organic crosslinked composite films using linear methyl methacrylate-co-glycidyl methacrylate (MG) as the matrix and ferroelectric poly(vinylidene fluoride) (PVDF) as the organic filler. The crosslinked MG networks can enhance the breakdown strength, restrain dielectric loss, and keep high discharge efficiency. What's more, the presence of PVDF can compensate for the low electrical displacement, improve the permittivity, and overcome the brittleness of the crosslinked films. The optimal all-organic crosslinked dielectric film exhibited an ultrahigh breakdown strength of 800 MV m-1 and a high efficiency of 77.4%. The maximum energy density of the composite film reached up to 12.1 J cm-3, which was nearly 120% higher than the energy density of 5.6 J cm-3 of the pure MG film. The enhancement in energy storage properties is ascribed to the synergistic effects of chemical crosslinking and hydrogen bonding. This study offers a feasible method for all-organic polymer films to fabricate energy storage equipment.