Orange peel waste (OPW), as a relevant and recoverable residue, is composed of peel, internal tissue, pulp, and seeds. This organic residue is rich in carbohydrates useful for biofuel production processes. Biohydrogen is obtained from dark fermentation (DF) and photofermentation (PF), which are complementary in the bioprocessing chain. The objective of this work was to compare the environmental impact assessment of a sequential dark–photofermentation process (Scenario DF-PF) and the individual fermentation processes: dark fermentation (Scenario DF) and photofermentation (Scenario PF). The assessment was performed at a laboratory scale, and the functional unit (FU) was defined as the production of 1 kg H2. Scenario DF showed the lowest environmental impacts regarding global warming and fossil resource scarcity indicators, with 375.5 kg CO2-eq/FU and 108.8 kg oil-eq/FU, respectively, followed by Scenario DF-PF and Scenario PF. Scenario DF-PF presented the lowest impact regarding the water consumption indicator (7.6 m3/FU), followed by Scenario DF, which had 46.6% more impact. Additionally, Scenario DF-PF required 3.3 times less substrate than Scenario DF due to more efficient substrate conversion. The high share of fossil fuels in the Mexican electricity mix directly impacts the processes that require electric energy, such as the PF process. Therefore, eco-friendly light sources should be used to minimize effects. Valorization of OPW could follow two routes depending on whether the aim is to reduce a specific environmental impact indicator or biowaste conversion efficiency.