The use of lignocellulosic biomass (LCB) as feedstock has received increasing attention as an alternative to fossil-based refineries. Initial steps such as pretreatment and enzymatic hydrolysis are essential to breakdown the complex structure of LCB to make the sugar molecules available to obtain bioproducts by fermentation. However, these steps increase the cost of the bioproduct and often reduces its competitiveness against synthetic products. Currently, the use of surfactants has shown considerable potential to enhance lignocellulosic biomass processing. This review addresses the main mechanisms and role of surfactants as key molecules in various steps of biorefinery processes, viz., increasing the removal of lignin and hemicellulose during the pretreatments, increasing enzymatic stability and enhancing the accessibility of enzymes to the polymeric fractions, and improving the downstream process during fermentation. Further, technical advances, challenges in application of surfactants, and future perspectives to augment the production of several high value-added bioproducts have been discussed.