Two-stage process of dark fermentation (DF) and photo fermentation (PF), using fruit and vegetable waste (FVW) and cheese whey powder (CWP), was used as an approach to enhance the hydrogen (H2) production. FVW and CWP at C/N ratios of 34, 39, 60, 71 and 82 were tested as substrates for DF. Dilution (1:2, 1:5, 1:10) of the DF effluents was used as a coupling strategy. DF effluents with low-butyrate and high lactate concentrations were obtained as a function of an increased C/N ratio, which results in high H2 production during the PF. Maximum overall H2 yields of 793.7 and 695.4 mLH2/gChemical Oxygen Demand (COD) were obtained using a 1:10 dilution, at a C/N ratio of 60 and 70, respectively. These H2 yields were higher than those obtained with the individual processes. The C/N ratio at the DF stage regulate not only H2 production but also the distribution and concentrations of by-products. These metabolites, in turn, control the H2 production during the PF. Predominant microbial population for both processes (DF: C/N = 34 Acetobacter lovaniensis, Clostridium butyricum; C/N = 39 C. butyricum, Enterobacter sp, Bifidobacterium; C/N = 82 Lactobacillus casei; PF: Rhodopseudomonas palustris) were in accordance with the final metabolic products. Display omitted •Enhanced H2 production by dark-photo (DF-PF) fermentations was demonstrated.•Fruit and vegetable waste and cheese whey as substrate allows waste removal and H2 production.•Increased C/N ratio reduces H2 yield at DF, but increase the H2 production at PF.•DF effluents with high lactate concentrations promotes high H2 production at PF.•Microbial population for both DF, PF in accordance with the final metabolic products.