Sugarcane press mud was pretreated by liquid hot water (LHW) at different temperatures (140–210 °C) and pre-treatment times (5–20 min) in order to assess the effects on the chemical oxygen demand (COD) solubilisation, inhibitors formation and methane yield. The experimental results showed that a high degree of biomass solubilisation was possible using LHW. Higher methane yields were obtained at lower severities (log(R_o) = 2.17–2.77) with (i) mild temperatures (140–150 °C) and long contact times (12.5 min, 20 min) or (ii) mild temperatures (175 °C) with short contact time (2 min). The highest increase in methane yield (up to 63%) compared to the untreated press mud was found at 150 °C for 20 min. At temperatures of 200 °C and 210 °C, low methane efficiency was attributed to the possible formation of refractory compounds through the Maillard reaction.