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Abstract The increasingly severe energy crisis has strengthened the determination to develop environmentally friendly energy. And hydrogen has emerged as a candidate for clean energy. Among many hydrogen generation methods, biohydrogen stands out due to its environmental sustainability, simple operating environment, and cost advantages. This review focuses on the rational design of catalysts for fermentative hydrogen production. The principles of microbial dark fermentation and photo‐fermentation are elucidated exhaustively. Various strategies to increase the efficiency of fermentative hydrogen production are summarized, and some recent representative works from microbial dark fermentation and photo‐fermentation are described. Meanwhile, perspectives and discussions on the rational design of catalysts for fermentative hydrogen production are provided.