Transportation and electric power generation are essential elements of a modern, mechanized agricultural system that can ensure adequate food supply. Yet, this crucial sector, which drives national development, faces a dual challenge: the high cost and environmental unfriendliness of conventional fuels used for transport and power production. In this work, several blends of Cape Verde biodiesel—80/20%, 60/40%, 40/60%, 20/80%, and 100%—were tested on a laboratory-scale, single-cylinder, direct-injection diesel engine under hybrid operation, to assess short-term performance and determine key operational parameters at four load conditions. The Cape Verde biodiesel complied with EN, BIS, and Brazilian biodiesel standards. The results showed that conventional diesel (reference fuel) delivered better performance than the Cape Verde biodiesel blends in terms of brake specific fuel consumption, brake thermal efficiency, and air–fuel ratio. Conversely, the Cape Verde biodiesel blends exhibited improved performance in engine and exhaust gas temperatures. Diesel and the B20 blend recorded almost identical values for brake power and volumetric efficiency. In addition, B100 produced the lowest engine temperature among all biodiesel blends and diesel fuel. Overall, B20 emerged as a promising candidate to replace conventional diesel, provided that long-term performance, combustion, and emissions studies confirm no issues related to engine starting, wear, compatibility with engine components, or catastrophic failure.