Food waste (FW) valorization through resource recovery is central to circular economy strategies that reduce environmental burden while generating sustainable, bio-based chemicals. This work investigated the effect of anaerobic sludge inoculum and the process control parameters of temperature (35 °C and 55 °C), pH value (4–10), and total solids content (2.5%, 5%, 7.5% and 10%) on the recovery of volatile fatty acids (VFAs)—chemicals used in bioplastics and bioenergy production—during acidogenic fermentation of food waste in batch reactors. While FW is well studied for biogas production, its potential for VFA recovery, a strategy that adds economic value to waste streams and supports the circular bioeconomy, remains comparatively underexplored. Mesophilic conditions favored fermentation over thermophilic conditions, and pH was the most influential factor affecting VFA accumulation, although temperature, inoculum presence, and total solids content also had statistically significant, large effects. Basic pH values provided maximum VFA yields from 2% to 25%, roughly double the acidic pH yields, while the highest solids content (10%) minimized VFA production at both temperatures. The highest yield (25%) occurred at T = 35 °C, pH 9, and TS = 5%, without sludge, while the highest yield under thermophilic conditions (T = 55 °C) reached 22.4% at TS = 2.5% and pH 9. By systematically evaluating these parameters together, this study offers a more comprehensive understanding of FW acidogenic fermentation than prior single-parameter works, guiding bioprocess design for sustainable waste management and resource efficiency.