The native form of lignocellulosic biomass is resistant to enzymatic breakdown. A well-designed pretreatment that can promote enzymatic hydrolysis of biomass with reasonable processing cost is therefore necessary. To this end, a number of different types of pretreatment technologies have been developed with a common goal of making biomass more susceptible to enzymatic saccharification. Among those, a pretreatment method using alkaline reagent has emerged as one of the most viable process options due primarily to its strong pretreatment effect and relatively simple process scheme. The main features of alkaline pretreatment are that it selectively removes lignin without degrading carbohydrates, and increases porosity and surface area, thereby enhancing enzymatic hydrolysis. In this review, the leading alkaline pretreatment technologies are described and their features and comparative performances are discussed from a process viewpoint. Attempts were also made to give insights into the chemical and physical changes of biomass brought about by pretreatment.