ConspectusGraphitic carbon nitride-based materials have emerged as promising photocatalysts for a variety of energy and environmental applications owing to their "earth-abundant" nature, structural versatility, tunable electronic and optical properties, and chemical stability. Optimizing carbon nitride's physicochemical properties encompasses a variety of approaches, including the regulation of inherent structural defects, morphology control, heterostructure construction, and heteroatom and metal-atom doping. These strategies are pivotal in ultimately enhancing their photocatalytic activities. Previous reviews with extensive examples have mainly focused on the synthesis, modification, and application of carbon nitride-based materials in photocatalysis. However, there has been a lack of straightforward and in-depth discussion to understand the electronic characteristics and functions of various engineered carbon nitrides as well as their precise tailoring strategies and ultimately to explain the regularity and specificity of their improved performance in targeted photocatalytic systems. In the past ten years, our group has conducted extensive investigations on carbon nitride-based materials and their application in photocatalysis. These studies demonstrate the close yet intricate relationship between the electronic structure of carbon nitride materials and their photocatalytic reactivity. Understanding the electronic structure and functions of carbon nitride, as well as different engineering strategies, is essential for the improvement of photocatalytic processes from fundamental study to practical applications.To this end, in this Account, we first delve into the nature of the electronic properties of carbon nitride, highlighting the electronic structures, including band structure, density of states, molecular orbitals, and band center, as well as its electronic functions, such as the charge distribution, internal electric field, and external electric force. Subsequently, based on recent research in our group, we present a detailed discussion of the strategic modifications of carbon nitride and the consequential impacts on the physicochemical properties, particularly the optical properties and intrinsic electronic characteristics, for enhancing the photocatalytic performance. These modifications are categorized as follows: (i) component changing, which involves intralayer and interface heterojunctions as well as homojunctions, to modulate the band-edge potentials and reactivity of photoinduced electrons and holes toward surface redox reactions; (ii) dimensional tuning, which engineers the dimensional structure of carbon nitride, to influence the electron transfer direction; (iii) defect and heteroatom modification, which introduces a symmetry break in the carbon nitride framework, to promote charge redistribution for altering the charge density and electronic structure; and (iv) anchoring of single-atom metals to facilitate orbital hybridization and charge transfer enhancement through the unique metal-N coordination configurations. Finally, we propose an appraisal of the prospects and challenges in the precise manipulation and characterization of the electronic structure and functions of carbon nitride. The integration of electronic structure analysis, theoretical calculation based on machine learning, and precise mechanism study may propel its substantial development in the light-driven circular economy. We hope this Account aspires to offer novel insights and perspectives into the operational mechanisms and tailored structure of carbon nitride-based materials in photocatalysis.