Food waste (FW) collected from a university canteen was treated in acidogenic fermenters to produce volatile fatty acids (VFA) under biological pretreatment with mature compost. Batch assays working at pH 6 revealed an increment of 9.0%, 7.9%, and 4.1% (on COD basis) of VFA concentration when adding 2.5%, 3.5%, and 4.5% w/w of mature compost, respectively, even though the volatile solids (VS) concentration of food waste was lower in the tests with increasing doses of mature compost. For batch tests at pH 7, this VFA generation improvement was lower, even though enhanced COD solubilization was recorded. Operating in semi-continuous conditions at 35 ºC, pH of 6, and hydraulic retention time (HRT) of 3.5 days, the addition of 2.5% w/w of mature compost led to a VFA concentration up to 51.2 ± 12.3% more (on VS basis) when compared to a reference reactor without compost addition. Moreover, the percentage of butyric acid on VS basis in the fermentation broth working at a pH of 6 increased from up to 12.2 ± 1.9% (0% compost addition) to up to 23.5 ± 2.7% (2.5% compost addition). The VFA production was not improved when a higher percentage of mature compost was used (3.5% instead of 2.5% w/w), and it slightly decreased when mature compost addition was lowered to 1.5% w/w. When working at a pH of 7 in the semi-continuous fermenters with the addition of 2.5% w/w mature compost at an HRT of 3.5 days, an improvement of 79% and 104% of the VFA concentration (on VS basis) were recorded as compared to fermenters working at a pH of 6 with 2.5% and 0% w/w of mature compost addition, respectively. At a pH of 7, higher production of propionic and valeric acids was found with respect to the reactor working at a pH of 6. The effect of pH on VFA generation was estimated to have greater contribution than that of only biological pretreatment using mature compost. At a pH of 7, the VFA yield was higher for the fermenter working with 2.5% w/w mature compost but at a pH of 7 and HRT of 5 days, the effect of mature compost on VFA production improvement was lower than that obtained at a pH of 6. Moreover, higher solubilization in terms of soluble chemical oxygen demand and total ammonium was detected when biological pretreatment using mature compost was applied at both a pH of 6 and a pH of 7, which indicates enhanced hydrolysis in both conditions.