MSW with an 8-day pre-aeration produced the highest biogas yield of 192.4 NL/kg DM. Butyric acid dominated the VFAs (50–55%) in over acidifying reactors during dry AD. Accelerated protein degradation by pre-aeration neutralized excessive VFAs. Pre-aeration facilitated the conversion of protein- to fulvic- and humic-like matter. Fulvic- to protein-like fluorescent matter ratio can evaluate the stability of dry AD.