Burning rice straw to dispose of it harms the environment, but it holds promise as a valuable resource for biofuel production due to its lignocellulosic content. Biofuels derived from diverse lignocellulosic sources, including agricultural residues, forest byproducts, and wood, offer sustainable alternatives or supplements to gasoline. Rice straw, abundant and renewable, stands out as a prime candidate for bioethanol production due to its high cellulose and hemicellulose content, convertible into fermentable sugars via hydrolysis. However, unlocking these sugars requires pretreatment to disrupt the lignin barrier and expose the cellulose and hemicellulose for enzymatic conversion. Pretreatment methods aim to reduce cellulose crystallinity, increase biomass surface area, remove hemicellulose, and break down lignin barriers. This review delves into various pretreatment approaches for rice straw, encompassing physical, physicochemical, chemical, and biological methods. Highlighting the critical role of pretreatment, the subsequent enzymatic hydrolysis stage involves breaking down cellulose and hemicellulose polymers into fermentable sugars enzymatically.