Biofuels are increasingly important renewable resources in the world’s energy matrix that have challenged the scientific community as well as small and large farmers to develop alternatives to fossil fuels in order to achieve the aims of energy transition. In particular, Brazil’s proven competitiveness in agribusiness together with its rich biodiversity put the country in a key position in the biofuels market. The semiarid Caatinga of northeastern Brazil, an exclusive biome rich in many oilseed species suitable for potential energy purposes, is of particular interest in this field. Nowadays, soybeans are the main feedstock used for the production of biodiesel, but, due to the increasing demand for biofuels, the search for alternative sources of oil from tropical flora with high productivity is crucial. Under this premise, this systematic review focuses on mapping Caatinga’s vegetable oil crops that could be used as alternative raw materials for biofuels’ production in Brazil, in addition to traditional soybeans and sugarcane. To gain more detailed insight into these matrices, their main properties, including oil content, fatty acid profile and physicochemical properties, are discussed. Moreover, an overview is provided of processes to synthesize different types of biofuels, particularly biodiesel and aviation biokerosene, including the routes employing homogeneous, enzymatic and mainly heterogeneous catalysts. Finally, future prospects and challenges for renewable biofuels and the Caatinga biome are addressed.