Lignocellulose and starch-based raw materials are often applied in the investigations regarding biohydrogen generation using dark fermentation. Management of the arising post-fermentation broth becomes a problem. The Authors proposed sequential processes, to improve the efficiency of both hydrogen generation and by-products management carried under model conditions. During the proposed procedure, the simple sugars remaining in broth are converted into organic acids, and when these products are used as substrates for the photo fermentation process. To enhance the broth management also conditions promoting Deep Eutectic Solvents (DES) precursors synthesis are simultaneously applied. Application of Box-Behnken design allows defining of the optimal conditions for conversion to DESs precursors. During the procedure hydrogen was obtained, the concentration of hydrogen in the photo fermentation reached up to 819 mL H2/L medium/7 d, depending on the broth type, i.e., when the broth was optimized for formic acid concentration. The DESs precursors were separated and engaged in DESs synthesis. To confirm the formation of the DESs, FT-IR analyses were performed. The Chemical Oxygen Demand of post-fermentation broths after dark fermentation optimized for formic acid was reduced by ca. 82%. The proposed procedure can be successfully used as a method of post-fermentation broth management.