Tannery sludge is disposed of in landfills as it is considered a special residue by the Italian legislation, creating pollution and waste. This paper aims at evaluating the performance of the anaerobic fermentation process to obtain short-chain fatty acids (SCFAs) from this waste. The assessment of the most appropriate conditions, in terms of pH, temperature, initial total solids (TSs) content, and application of oxidizing-thermal pretreatment has been developed. The batch test trials revealed that the combined microwave and hydrogen peroxide (MW-H2O2) pretreatment followed by thermophilic conditions gave the best results, in terms of the acidification yield (0.31 gCODSCFA/gVS0) and maximal SCFA concentration (above 26 g CODSCFA/L). In the tests conducted without pretreatment, the mesophilic temperature should be preferred since the acidification performances were comparable to or even better than their thermophilic counterparts. The SCFA composition analysis showed that in mesophilic fermentation, tannery sludge can generate up to 50% acetic acid (CODAc/CODSCFA), if previously pretreated (MW-H2O2). This research acts as a forerunner for the appropriate handling of this resource, to employ it for the development of a new tannery industry focused on a circular approach, rather than to simply dispose of it in landfills.