Biogas plants for waste treatment valorization are presently experiencing rapid development, especially in the agricultural sector, where large amounts of digestate are being generated. In this study, we investigated the effect of vibro-ball milling (VBM) for 5 and 30 min at a frequency of 20 s−1 on the physicochemical composition and enzymatic hydrolysis (30 U g−1 total solids (TS) of cellulase and endo-1,4-xylanase from Trichoderma longibrachiatum) of dry and wet solid separated digestates from an agricultural biogas plant. We found that VBM of dry solid digestate improved the physical parameters as both the particle size and the crystallinity index (from 27% to 75%) were reduced. By contrast, VBM of wet solid digestate had a minimal effect on the physicochemical parameters. The best results in terms of cellulose and hemicelluloses hydrolysis were noted for 30 min of VBM of dry solid digestate, with hydrolysis yields of 64% and 85% for hemicelluloses and cellulose, respectively. At the condition of 30 min of VBM, bioethanol and methane production on the dry solid separated digestate was investigated. Bioethanol fermentation by simultaneous saccharification and fermentation resulted in an ethanol yield of 98 geth kg−1 TS (corresponding to 90% of the theoretical value) versus 19 geth kg−1 TS for raw solid digestate. Finally, in terms of methane potential, VBM for 30 min lead to an increase of the methane potential of 31% compared to untreated solid digestate.