•Efficiency of anaerobic digestion is hampered due to microalgae cell wall.•Improved biodegradability was achieved by all the evaluated pretreatments.•Thermal treatment for 40min and 120°C supported the highest methane production.•Higher biomass concentration is required to obtain a positive energy balance. To enhance the anaerobic digestion of Chlorella vulgaris, thermochemical pretreatments were conducted. All pretreatments markedly improved solubilisation of carbohydrates. Thermal treatments and thermal treatments combined with alkali resulted in 5-fold increase of soluble carbohydrates while thermal treatment with acid addition enhanced by 7-fold. On the other hand, proteins were only solubilized with thermo-alkaline conditions applied. Likewise, all the pretreatments tested improved methane production. Highest anaerobic digestion was accomplished by thermal treatment at 120°C for 40min without any chemical addition. As a matter of fact, hydrolysis constant rate was doubled under this condition. According to the energetic analysis, energy input was higher than the extra energy gain at the solid concentration employed. Nevertheless, higher biomass organic load pretreatment may be an option to achieve positive energetic balances.