In this research work, the feasibility of using fusel oil, a by-product of the sugar–alcohol industry, as an LVLC solvent in blends with straight vegetable oils (SVOs) and diesel was investigated. Concretely, diesel/fusel oil/sunflower oil (D/FO/SO) and diesel/fusel oil/castor oil (D/FO/CO) triple blends were prepared and characterized by measuring the most important physicochemical properties, i.e., viscosity, density, cold flow properties, flash point and cetane number. An appreciable improvement in cold flow values has been achieved with triple blends, without compromising properties such as calorific value and cetane number. Likewise, the triple blends meet the viscosity and density requirements specified by the European quality standard EN 14214 and the American standard ASTM D6751. After characterization, the triple blends were used on a diesel engine, evaluating different parameters such as power output, opacity, exhaust emissions (CO and NOx) and consumption at different engine loads. The results indicate that as the biofuel content in the blend increases, engine power decreases while fuel consumption rises. Nevertheless, the values obtained with D/FO/CO are better than those for D/FO/SO and are also very similar to those of fossil diesel. Regarding opacity values and NOx emissions obtained with the utilization of the triple blends, they are lower than those produced by diesel. However, in the case of CO emissions, it depends on the type of oil used, with the samples prepared with castor oil exhibiting the best results.