This study investigates the dark fermentation of fruit and vegetable waste under mesophilic conditions (30−34 °C), as a valorization route for H2 and volatile fatty acids production, simulating the open market waste composition over the year in two Mediterranean countries. Specifically, the study focuses on the effect of the (i) seasonal variability, (ii) initial pH, and (iii) substrate/inoculum ratio on the yields and composition of the main end products. Concerning the seasonal variation, the summer and spring mixtures led to +16.8 and +21.7% higher H2 production than the winter/autumn mixture, respectively. Further investigation on the least productive substrate (winter/autumn) led to 193.0 ± 7.4 NmL of H2 g VS−1 at a pH of 5.5 and a substrate/inoculum of 1. With the same substrate, at a pH of 7.5, the highest acetic acid yield of 7.0 mmol/g VS was observed, with acetic acid corresponding to 78.2% of the total acids. Whereas a substrate/inoculum of 3 resulted in the lowest H2 yield, amounting to 111.2 ± 7.6 NmL of H2 g VS−1, due to a decrease of the pH to 4.8, which likely caused an inhibitory effect by undissociated acids. This study demonstrates that dark fermentation can be a valuable strategy to efficiently manage such leftovers, rather than landfilling or improperly treating them.