<p>Lignocellulosic biomass, a renewable raw material for producing biobased products, has attracted significant attention in biorefinery. To efficient deconstruct the complex components in lignocellulose, development of pretreatment technologies is a key research focus. Practically, use of cost-effective and easily recyclable solvent to achieve high fractionation and enzymatic hydrolysis efficiency could prompt the valorization of lignocellulose. With the excellent nucleophilicity and reactivity, amine compounds have shown remarkable advantages in lignocellulose pretreatment. Hence, this review summarizes recent amine-based pretreatment strategies to explore their key roles in lignocellulose structural deconstruction, enhancement of sugar yields, and fermentability of substrates for biobased chemical production. Firstly, the effects of amine compounds on lignin removal, cellulose crystalline structure transformation, and improvement in enzymatic hydrolysis are reviewed. Subsequently, progress in synergistic pretreatment combining amine solvents with green systems such as ionic liquids, surfactants, and mechanical assistance is summarized, demonstrating the potential of integrated approach to enhance biomass fractionation, preserve lignin structure, and increase fermentable sugar yields. Meanwhile, this review also discusses the application of solid and liquid fractions obtained from amine-based pretreatment in microbial fermentation to produce bioethanol, L-lactic acid, and biobutanol. Finally, challenges remain in by-product control and solvent recovery in amine-based pretreatment, and prospects for its development in future biorefinery are systematically provided. Overall, amine-based pretreatment offers a sustainable pathway for efficient deconstruction and valorization of lignocellulose.</p>