Pollution generated by agro industrial waste—composed of esters, fatty acids, and alcohols—is a significant environmental concern due to its impact on air quality, greenhouse gas emissions, and soil contamination. Given this problem, there has been growing interest in finding alternative uses to mitigate its negative effects. One promising application of this waste is its use in the pretreatment of lignocellulosic biomass, where it can facilitate the decomposition of plant materials for biofuel production. Among the most commonly used pretreatment methods are acids, alkalis, ionic liquids, and eutectic solvents, which improve the efficiency of enzymatic hydrolysis. Lignocellulosic biomass, being an abundant renewable resource, has great potential for obtaining high-value biochemical products. However, for its optimal utilization, treatments that improve its structural accessibility are necessary. The interaction between waste and biomass not only improves the decomposition of plant fibers but also represents a way to increase the sustainability of industrial processes. This synergy between agro-industrial waste and bioenergy technologies could mark a significant advance in the efficient production of biofuels, contributing to reducing environmental impact and promoting a greener circular economy.