Hydrothermal liquefaction (HTL) is a promising thermo-chemical technology for municipal sludge treatment due to its potential for biocrude oil recovery and minimizing biosolids management costs. However, the process generates a high volume of an aqueous byproduct that needs to be treated due to its high chemical oxygen demand (COD) and various organic and inorganic compounds. Although the aqueous phase is known to contain recalcitrant and potentially inhibitory substances that may affect its biological treatment, their molecular weight distribution (MwD) and its impact on anaerobic biodegradability are poorly understood. Ultrafiltration (UF) was conducted to fractionate HTL aqueous into different molecular weight (Mw) fractions using 300, 100, 10, and 1 kDa membranes. Mesophilic biochemical methane potential (BMP) assays were conducted to assess the anaerobic biodegradability of each fraction, and the first-order model was used to calculate the degradation kinetics of potential inhibitory compounds. The highest percentage of organics (65 %) was found in the Mw<1 kDa range, whereas the 10>Mw>1 kDa had the lowest percentage (8 %). There was no significant difference in the cumulative specific methane produced from various Mw fractions (p>0.05). The Mw<1 kDa fraction had the highest first-order specific methane production rate (0.53 day−1), whereas the unfiltered HTL had the lowest (0.38 day−1). Although UF fractionation increased the rate of anaerobic degradation of HTL aqueous for the Mw<1 kDa fraction, the observed methane potential was only 55 % of the theoretical value. This implies that 45 % of COD remains undegraded even after permeation through the lowest Mw cut-off membrane. Therefore, further characterization of HTL aqueous is needed for compounds with molecular weights below 1 kDa to fully understand the nature of inhibitory organics and their impact on anaerobic digestion. Furthermore, pretreatments utilizing techniques such as adsorption and advanced oxidation may be necessary to enhance the specific methane yields from various HTL aqueous fractions, thereby bringing them closer to the theoretical yield.