Amid the urgent demand for eco-friendly and renewable energy solutions, hydrogen emerges as a compelling substitute for traditional fossil fuels. This review aims to guide researchers and policymakers by critically assessing semiconductor-based photocatalysts for sustainable hydrogen production. The methodology involved a systematic examination of approximately 85 publications, focusing on photophysical properties, photocatalytic efficiency, and stability. The novelty of this work lies in its integration of quantitative performance indicators with comparative evaluation, offering both numerical benchmarks and contextual insights. Among the materials studied, titanium dioxide (TiO₂) demonstrates the highest efficiency, achieving hydrogen generation rates up to 6715 μmol/g/h under UV light, while cadmium sulfide (CdS) delivers 500 μmol/g/h under visible light. This comparison illustrates TiO₂’s stability but UV-only activation versus CdS’s broader solar utilization but photocorrosion challenges. Other materials, such as ZnO (1200 μmol/g/h), Cu₂O (530 μmol/g/h), and BiVO₄ (1060 μmol/g/h), further highlight the trade-offs between efficiency, stability, and environmental impact. Beyond performance metrics, the environmental and economic benefits of semiconductor-based photocatalysts are discussed, underscoring their contributions to sustainable energy frameworks. The article also examines obstacles linked to scaling these materials, including cost, stability, and infrastructure requirements. Possible applications include hydrogen fuel cells for transportation, electricity generation, and industrial feedstocks such as steel and chemicals. By integrating numerical comparisons, methodological clarity, and application relevance, this review identifies the most advantageous materials and outlines future research trajectories for eco-friendly hydrogen production.