Efficient charge separation and transfer are crucial for elevating photocatalytic oxidation, and designing a photocatalyst structure with strong internal electric fields (IEF) hold promise for addressing the issue. Herein, we synthesized a silica-PDI (silica-perylene diimides) decorated vertical graphene (s-PDI@VG) architecture with an Acceptor-Donor-Acceptor (A-D-A) structure. The A-D-A configuration facilitated electron transfer from tertiary N-atom to perylene tetracarboxylic dianhydride (PTCDA) and flower-like vertical graphene (VG), resulting in a larger molecular dipole moment of s-PDI@VG compared to PTCDA and s-PDI. Consequently, an IEF with 7.5 times higher than PTCDA and 4.8 times higher than s-PDI was built, which is beneficial for photogenerated charge separation. Additionally, the valence band (VB) of s-PDI@VG deepened from 1.43 eV to 1.62 eV, enabling it to afford a strong oxidation potential. As a proof-of-concept, the 3D s-PDI@VG photocatalyst demonstrated favorable persulfate (PMS) activation and pollutant adsorption, resulting in 1.6 times higher photogenerated holes based on LSCM results. This photocatalyst also achieved 98.2 % mineralization of high-ionization-potential (h-IP) organics within 30 min. This work offers insights into a novel photocatalytic oxidation strategy with high mineralization by engineering A-D-A structure and enhancing the IEF strength of photocatalyst molecules.