This work is focused on optimising a low-temperature delignification as holocellulose purification pretreatment of Platanus acerifolia leaf waste for second-bioethanol production. Delig-nification was accomplished by acid-oxidative digestion using green reagents: acetic acid and 30% hydrogen peroxide 1:1. The effect of reaction time (30–90 min), temperature (60–90 ◦C), and solid loading (5–15 g solid/20 g liquid) on delignification and solid fraction yield were studied. The process parameters were optimised using the Box–Behnken experimental design. The highest attained lignin removal efficiency was larger than 80%. The optimised conditions of delignification, while maximising holocellulose yield, pointed to using the minimum temperature of the examined range. Analysis of variance on the solid fraction yield and the lignin removal suggested a linear model with a negative influence of the temperature on the yield. Furthermore, a negative effect of the solid loading and low effect of temperature and time was found on the degree of delignification. Then the temperature range was extended back to 60 ◦C, providing 71% holocellulose yield and 70% while improving energy efficiency by working at a lower temperature. Successful lignin removal was confirmed using confocal laser scanning microscopy. As evaluated by scanning electron microscopy, the solid structure presented an increased exposition of the cellulose fibre structure.