Sugarcane processing produces a significant amount of byproducts in the form of straw and bagasse, which are rich in cellulose, hemicellulose, and lignin. This work aims to provide a valorization approach to sugarcane straw by optimizing a two-step alkaline extraction of arabinoxylans by a response surface methodology to evaluate a potential industrial-scale production. Sugarcane straws were delignified using an alkaline–sulfite pretreatment, followed by alkaline extraction and precipitation of arabinoxylan, a two-step process optimized using a response surface methodology. A KOH concentration of (2.93–17.1%) and temperature (18.8–61.2 °C) were chosen as independent variables, and the arabinoxylan yield (%) as a response variable. The model application shows that KOH concentration, temperature, and the interaction between both independent variables are significant in extracting arabinoxylans from straw. The best-performing condition was further characterized by FTIR, DSC, and chemical and molecular weight evaluation. The straws arabinoxylans presented high purities levels, ca. 69.93%, and an average molecular weight of 231 kDa. The overall estimated production cost of arabinoxylan from straw was 0.239 €/g arabinoxylan. This work demonstrates a two-step alkaline extraction of the arabinoxylans method, as well as their chemical characterization and economic viability analysis, that can be used as a model for industrial scale-up production.