Pretreatment of lignocellulosic biomass to overcome its intrinsic recalcitrant nature prior to the production of valuable chemicals has been studied for nearly 200 years. Research has targeted eco-friendly, economical and time-effective solutions, together with a simplified large-scale operational approach. Commonly used pretreatment methods, such as chemical, physico-chemical and biological techniques are still insufficient to meet optimal industrial production requirements in a sustainable way. Recently, advances in applied chemistry approaches conducted under extreme and non-classical conditions has led to possible commercial solutions in the marketplace (e.g. High hydrostatic pressure, High pressure homogenizer, Microwave, Ultrasound technologies). These new industrial technologies are promising candidates as sustainable green pretreatment solutions for lignocellulosic biomass utilization in a large scale biorefinery. This article reviews the application of selected emerging technologies such as ionizing and non-ionizing radiation, pulsed electrical field, ultrasound and high pressure as promising technologies in the valorization of lignocellulosic biomass.