As part of the global energy transition towards more sustainable solutions, it is crucial to reduce dependence on fossil fuels by exploring renewable alternatives. This study focuses on the optimization of agricultural residues to develop biofuels for thermal power plants in Côte d’Ivoire. The raw materials studied come from rice, coffee and cocoa crops, which are abundant in rural areas of the country. The aim is to assess the feasibility of creating energy-efficient biofuels that are compatible with power plant boilers, while meeting environmental sustainability criteria. To achieve this, a linear programming model was used to determine the optimum proportions of the various agricultural residues to produce usable blends. The model considers higher heating value, the reduction of pollutant emissions and the preservation of combustion equipment. The energy performance of the fuels is then analyzed using a biomass power plant model. The results led to the development of two types of sustainable biofuel: the first, made up of 68% rice husk and 32% coffee husk, has a higher heating value of 13.79 MJ/kg; the second, made up of 60% rice husk and 40% cocoa pod husk, has a higher heating value of 13.49 MJ/kg. These biofuels stand out for their ability to reduce pollutant emissions and preserve combustion equipment. Rice straw is added to these two fuels to form the matrix of sustainable biofuels to produce electricity from a biomass power plant in Côte d’Ivoire. This study shows that it is possible to make effective use of agricultural residues to create sustainable biofuels, thereby contributing to a transition towards a more sustainable energy mix.