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Lignin contributes to the recalcitrance of lignocellulosic biomass and affects enzymatic activity during biorefinery operations. Therefore, it must be removed before further processing. Organic solvents (organosolv) and ionic liquids are two important pretreatments for delignifying lignocellulosic biomass. They have proven beneficial for fractionating and recovering cellulose and hemicellulose, as well as lignin with useful physicochemical properties. Volatility and harsh conditions of the acidic systems that result in toxicity, corrosion, and pollution are the main problems of organosolv. Ionic liquids, generally recognized as green solvents, have also been proposed as a possible solution to the challenge of using lignocellulosic biomass. Ionic liquids can either dissolve the lignocellulosic biomass completely or dissolve it into individual fractions. This review considers the advantages and disadvantages of organosolv and ionic liquids, since both are important methods to fractionate lignocellulosic biomass in their main components which can be converted into value added products.