Abstract Rapeseed straws are recoverable lignocellulosic biomass for second generation bioethanol production. Therefore, a pretreatment step is recommended in order to increase accessibility of enzymes to sugars. As a pretreatment step in this study, several innovative technologies have been performed in order to investigate their efficiency for delignification and enzymatic hydrolysis purposes: microwaves (MW), high voltage electrical discharges (HVED) and ultrasounds (US). As a key processing parameter, different levels of energy input were studied MW (1832–7328 kJ/kg), US (916–3664 kJ/kg) and HVED (204–814 kJ/kg) corresponding to a treatment duration range of 10–40 min. Treatment temperature (60–90 °C) and medium alkalinity (0.125–0.5 M) impact was also investigated and optimized based on sugar and soluble lignin contents in black liquor, and lignin removal yields. Delignification yields increased from 28.3%, 28.6% and 31.2% for 10 min of treatment to 38.4%, 41.5% and 42.3% for 40 min of treatment, respectively for MW, US and HVED. However, in order to achieve the same efficiency the energy required by HVED is 9 times and 4.5 times less than that required by MW and US respectively. Treatment temperature also revealed to be important as sugars yields increased by 41.6% when temperature increased from 60 °C to 90 °C for HVED and the optimal medium alkalinity was found to be 0.3 M. Finally, better enzymatic hydrolysis yields were obtained and correlated to better delignification performances improving material accessibility.