With a predominantly humid tropical climate and a large area for expanding agricultural activities, Angola has in principle favorable conditions for bioenergy production. The focus of this study was to evaluate the availability of suitable land for producing sugarcane. This crop is highly efficient in converting solar energy into biomass for energy purposes in Angola. To this end, this paper outlines a method for data collection, processing, and analysis divided into three sections. The first section uses the GAEZ (Global Agroecological Zones) database and QGIS (Quantum GIS) software (version 3.22.5) to assess land availability for sugarcane cultivation in Angola, classifying the regions’ suitability into four levels. The second section supplements this with data from the FAOSTAT database, systematically excluding areas with restrictions, such as protected zones, land already used for other crops, and regions unsuitable for sugarcane. Finally, the third section employs an agricultural yield model to estimate the potential yield of sugarcane based on climatic parameters and the amount of bioenergy (ethanol and bioelectricity) able to be produced in the available land. Under these criteria, this study identified the existence of 6.3 Mha in lands of good agricultural suitability, with water resources, corresponding to 5% of the Angolan territory, distributed in seven provinces of the country, especially in the provinces of Cuando Cubango and Cunene, where 85% of the very suitable land under irrigation is located. Adopting a model of agricultural productivity, assuming irrigation and adequate agricultural practices, such area could produce approximately 956 million tons of sugarcane annually, which is significantly higher than the current production in this country. This amount of feedstock processed using current technology could potentially produce 81.3 GL of ethanol and 176.9 TWh of electricity with low GHG emissions per year, which is able to mitigate, as a whole, circa 60.3 MtCO2-eq/year by displacing gasoline in light vehicles and diesel and natural gas consumed in power generation.