Melon (also known as graphitic carbon nitride, g‐C3N4) holds promise for photocatalysis, but challenges such as severe charge recombination, low oxidation potential, and sluggish exciton dissociation hinder its performance. Herein, a series of carbon‐rich, melon‐based photocatalysts are synthesized via one‐pot, temperature‐induced condensation of urea with the addition of a trace amount of citric acid. The addition of citric acid enhances crystallinity, extends melon chains, increases the C/N ratio, and improves π–π layer stacking of heptazine units, thereby enhancing charge transport properties and visible‐light harvesting capacity. These carbon nitride samples are then coupled with molten salt synthesized K4Nb6O17 crystals by a straightforward self‐assembly method to construct 2D/2D heterostructure photocatalysts. Z‐scheme electron transfer from K4Nb6O17 to the melon samples is established based on their work functions and band edge positions. This efficient charge transfer in the Z‐scheme heterostructure facilitates the spatial separation of charge carriers, resulting in a nearly fivefold enhancement in photocatalytic performance compared to the individual constituents.