To enhance deoxygenation and cracking of fatty acid methyl esters in jet fuel production, an efficient bifunctional catalyst was synthesized through pyrolyzing Ni-based metal–organic frameworks (Ni-BDC). High-temperature pyrolysis destroyed coordinated Ni–O bonds in the Ni-BDC structure to generate active Ni nanoparticles anchored to carbon, which enhanced Lewis acidity and deoxygenation ability. The strong acidity of catalyst pyrolyzed at 600 °C increased from 0 to 0.835 mmol/g, whereas the ratio of Lewis to Brønsted acid increased from 8.34 to 24.71. Therefore, the selectivity of jet-fuel-range hydrocarbons in methyl palmitate conversion over Ni-BDC-600 catalyst reached 83.52%, which was higher than that (68.24%) of Ni-BDC catalyst. The Ni-BDC-600 catalyst also exhibited a high selectivity of 75.56% for the conversion of microalgal biodiesel into jet fuel.