Colombia is a leading country in the production of palm oil, being the fourth in the world and the first in Latin America. However, large quantities of agro-industrial waste are produced from this industry, such as rachis, palm kernel shells, palm kernel cake, oily sludge, and sewage. Through this research, the aim is to find the most efficient route for obtaining bioethanol by taking advantage of a well-known, but not widely used, agro-industrial waste from the production of palm oil: palm kernel shells. This route must be convenient according to technical, economic, social, and environmental criteria of sustainability, for which the synthesis of routes of exploitation of the rachis based on optimization of superstructures will be implemented. In this work, a superstructure empathizing pretreatment stage was constructed with intermittent layers of chemical species required or obtained, and another of technologies for separation or transformation of said chemical species. Organosolv pretreatment (ethanol-acid) and thermochemical pretreatment (pyrolysis) were obtained as results: both routes were evaluated from the break-even point analysis to define which of them to choose as the most promising, giving as a final result the pyrolysis pretreatment.