In this work, 0.75 wt ‰ 2,3-pyridinedicarboxylic anhydride (PDA) as a novel dopant was utilized to obtain modified graphitic carbon nitride with ultratrace doping (3MCN-PDA 3 ) by facile thermal polymerization. Characterization of the microstructure, surface state, and porosity properties of the samples indicated that 3MCN-PDA 3 has a thinner sheet-like, larger-scale, and tighter lamellar stacking structure than that of pristine graphitic carbon nitride (3MCN). Based on photo/electrochemical analysis, the PDA dopant formed an extended coplanar conjugated system by anhydride-amine thermal condensation with heptazine rings, and the channels of amide covalent bonds and superconjugation of the solitary pair of electrons of the nitrogen atoms of PDA synergistically promoted the charge transport performance of 3MCN-PDA 3 . Under visible light, the photodegradation efficiency of Rhodamine B (RhB) over 3MCN-PDA 3 reached 92.4% in 60 min and realized almost entire removal in 200 min (99.2%), 1.43 times that of 3MCN. Furthermore, the experimental results and generalized density theory calculations confirmed that PDA acts as an intermediate molecular island and constructs an efficient carrier transfer pathway between different heptazine units. The results indicate that PDA is a promising candidate to enhance the charge transfer performance through ultratrace doping in the large-scale preparation and application of the graphitic carbon nitride photocatalyst.