By combining different semiconductors, scientists have developed innovative materials capable of converting solar energy into useful forms of energy or driving chemical reactions that clean up pollutants. These materials offer a promising path to combat global environmental and energy challenges. In this study, HAp@Bi2S3 core–shell structures were synthesized using a facile microemulsion technique, and then loaded onto graphitic carbon nitride via a hydrothermal method to create an advanced HAp@Bi2S3/g-C3N4 dual S-scheme heterojunction. The engineered heterojunction exhibited enhanced hydrogen production and visible light photocatalytic oxidation of metronidazole. The improved photocatalytic efficiency was attributed to the core–shell structure of HAp@Bi2S3 along with the formation of a dual S-scheme heterojunction in HAp@Bi2S3/g-C3N4. As a result, the novel dual S-scheme HAp@Bi2S3/g-C3N4 heterojunction demonstrated a significantly higher hydrogen production rate, ca. 20 times higher than that of hydroxyapatite (HAp), 11 times higher than Bi2S3, and 5 times higher than the HAp@Bi2S3. This research introduces a novel approach to crafting dual S-scheme heterojunctions based on Bi2S3, which enables swift electron transfer across heterojunction interfaces, thereby enlarged possibility windows to sustainable hydrogen production and wastewater remediation technologies.