Biomass‐based biofuel production is a promising solution to the decline of fossil fuels. Prosopis juliflora seed‐derived vegetable oil, known as Prosopis juliflora methyl ester (JFME), offers a potential feedstock for biodiesel. To enhance its properties, the addition of Decanol is investigated, a higher‐order alcohol similar to Diesel. Experiments are conducted on a 5.2 kW compression ignition (CI) engine using JFME blended with different decanol concentrations (5%, 10%, 15%, and 20%). Fourier‐transform infrared spectroscopy and gas chromatography‐mass spectrometry analysis confirm its compliance with fuel standards. The findings reveal that the 20% decanol blend (D20) achieves a brake thermal efficiency of 29.9% at full load, with reduced NO, smoke, and hydrocarbon (HC) emissions compared to diesel. D20 shows NO emissions of 1265 ppm, smoke opacity of 53%, and HC emissions of 69 ppm, while diesel records 1320 ppm, 69%, and 75 ppm, respectively. The CO emissions for D20 are 0.359 vol%, slightly higher due to decanol's higher latent heat of evaporation. Moreover, D20 exhibits improved combustion with a higher mass fraction burnt and faster heat release rates. These results indicate the potential of using JFME blended with 20% decanol as an alternative fuel for CI engines, offering higher performance and reduced emissions.