Lignocellulosic biomass is one of the potential feedstocks to produce second-generation cellulosic ethanol and biochemicals. To enhance the enzymatic digestibility of lignocellulosic biomass for efficient enzymatic saccharification, a variety of pretreatment methods have been studied. Among these, organosolv pretreatment using ethanol is a promising pretreatment method owing to its inherent advantages, such as low solvent cost, lack of toxicity, the ability to retain most cellulose fraction in substrates for enzymatic hydrolysis, coproduction of high-purity lignin and hemicellulosic sugars, easy solvent recovery, and reuse. In this review, the research progress regarding different types of ethanol organosolv pretreatment processes has been summarized in terms of methods, substrate properties, reaction mechanisms, delignification kinetic as well as the impact of pretreatment methods on the enzymatic digestibility. Attempts are also made to provide insights into the complete utilization of lignocellulosic biomass to achieve high potential revenues. Though some ethanol organosolv processes have been studied or are being developed towards commercialization, ethanol organosolv pretreatment is still facing some challenges. Finally, the direction for future work is given to develop a proper ethanol organosolv pretreatment for commercialization.