Volatile fatty acids (VFAs) are regarded as building blocks with a wide range of applications, including biofuel production. The traditional anaerobic digestion used for biogas production can be alternatively employed for VFAs production. The present study aimed at maximizing VFAs productions from Chlorella vulgaris through anaerobic digestion by assessing the effect of stepwise organic loading rates (OLR) increases (3, 6, 9, 12 and 15 g COD L-1 d-1). The biological system was proven to be robust as organic matter conversion efficiency into VFAs increased from 0.30 ± 0.02 COD-VFAs/CODin at 3 g COD L-1 d-1 to 0.37 ± 0.02 COD-VFAs/CODin at 12 g COD L-1d-1. Even though, the hydrolytic step was similar for all studied scenario sCOD/tCOD = 0.52-0.58), the highest OLR (15 g COD L-1 d-1) did not show any further increase in VFAs conversion (0.29 ± 0.01 COD-VFAs/CODin). This fact suggested acidogenesis inhibition at 15 g COD L-1d-1. Butyric (23-32%), acetic (19-26%) and propionic acids (11-17%) were the most abundant bioproducts. Population dynamics analysis revealed microbial specialization, with a high presence of Firmicutes followed by Bacteroidetes. In addition, this investigation showed the microbial adaptation of Euryarchaeota species at the highest OLR (15 g COD L-1d-1), evidencing one of the main challenges in VFAs production (out-competition of archaea community to avoid product consumption). Stepwise OLR increase can be regarded as a tool to promote VFAs productions. However, acidogenic inhibition was reported at the highest OLR instead of the traditional hydrolytic barriers. The operational conditions imposed together with the high VFAs and ammonium concentrations might have affected the system yields. The relative abundance of Firmicutes (74%) and Bacteroidetes (20%), as main phyla, together with the reduction of Euryarchaeota phylum (0.5%) were found the best combination to promote organic matter conversion into VFAs.