In this study, two different organic fractions of municipal solid waste (OFMSW) served as raw material in a novel treatment process that combines thermal hydrolysis (TH) pretreatment at different times, followed by anaerobic digestion of the solid fraction and photo-fermentation of the liquid fraction. The results indicate that both wastes performed similarly, and no statistically relevant differences stand out on the overall performance regarding TH times. The thermal pretreatment improves the biodegradability of the solid fraction during anaerobic digestion compensating the loss of the organic matter in the liquid fraction. The produced biogas may feed a combined heat and power (CHP) system, making the process energetically positive in all studied scenarios. In addition, the combination of TH and anaerobic digestion decreased the volume of the waste to be disposed by 59–61%, which is 5–11% higher than that obtained with the traditional treatment of anaerobic digestion process. Specific phototrophic activity tests were performed on the liquid phase using a mixed culture of purple phototrophic bacteria (PPB) that consumed up to 80% of the soluble organics. The assays yielded an average 52% efficiency on specific phototrophic activity (kM) and 62% on biomass yield (YX/S), compared to an optimized growth medium. PPB was also capable of producing polyhydroxyalkanoates, bioH2 and single-cell protein without optimization. Apart from methane, the overall mass balances showed yields up to 150 g of high added-value products per Kg of initial total solids on this proof-of-concept platform.