The global proliferation of plastic waste has made the search for sustainable chemical recycling strategies imperative to transition toward a circular bioeconomy. This study presents a dual-valorization approach for polylactic acid (PLA) waste, utilizing it both as a sustainable precursor for g-C₃N₄ catalyst synthesis and as a sacrificial agent for green hydrogen production via photoreforming. Platinum-modified graphitic carbon nitride catalysts were synthesized and evaluated using pure lactic acid and commercial PLA waste under solar-simulated irradiation. Results identified C₃N₄-NaOH-Pt as the most active material, while the simultaneous one-pot depolymerization/photoreforming of macroscopic PLA fragments exhibited a peak H₂ production rate of 1.5 mmol·h⁻¹·g⁻¹, remarkably surpassing both the pure monomer model and pre-depolymerized solutions. This enhanced performance is tentatively attributed to a “controlled release” mechanism that prevents catalyst surface saturation and minimizes light scattering effects inherent to fine powders. The study concludes that maintaining the macroscopic integrity of PLA waste provides a strategic advantage for chemical reforming by eliminating energy-intensive grinding and pretreatment. Future research into diverse operational and chemical parameters, including temperature and base-addition strategies, will be essential for scaling solar-driven upcycling technologies.