Hydrothermal liquefaction is a process that converts wet biomass into biofuels, more specifically bio-crude oil. During the process, post hydrothermal liquefaction waste water (PHWW) is generated, rich in nutrient and organic matter, however potentially toxic. Anaerobic digestion of PHWW from Spirulina, was evaluated using biostimulated sludge as a strategy to optimize the process. The biostimulation was conducted in a sequential batch reactor fed with organic acids and methanol aiming at development of acetogenic and methanogenic microorganism. Anaerobic biodegradability batch assays were performed, with biostimulated sludge and with non-biostimulated sludge, using increasing PHWW concentrations. Biostimulated sludge were more favourable for reaching higher methane yields at higher organic matter concentrations in comparison to non-biostimulated sludge, presenting less inhibition at conditions tested. Biostimulation was a key process to select and favour potential microorganisms involved in specialized uptake of recalcitrant compounds, such as Mesotoga and Methanomethylovorans.