The aim of this study is to investigate the performance of a pilot-scale plug-flow reactor (PFR) as a biorefinery system to recover chemicals (i.e., volatile fatty acids (VFAs)), and biogas during the dry thermophilic anaerobic digestion (AD) of the organic fraction of municipal solid waste (OFMSW). The effects of the hydraulic retention time (HRT) on both outputs were studied, reducing the parameter from 22 to 16 days. In addition, VFA variation along the PFR was also evaluated to identify a section for a further valorization of VFA-rich digestate stream. A particular focus was dedicated for characterizing the community responsible for the production of VFAs during hydrolysis and acidogenesis. The VFA concentration reached 4421.8 mg/L in a section located before the end of the PFR when the HRT was set to 16 days. Meanwhile, biogas production achieved 145 NLbiogas/d, increasing 2.7 times when compared to the lowest HRT tested. Defluviitoga sp. was the most abundant bacterial genus, contributing to 72.7% of the overall bacterial population. The genus is responsible for the hydrolysis of complex polysaccharides at the inlet and outlet sections since a bimodal distribution of the genus was found. The central zone of the reactor was distinctly characterized by protein degradation, following the same trend of propionate production.