Pyrolysis and cracking of vegetable oils are acceptable processes. Alkali-treated (NaOH) aluminium oxide (Al2O3) catalyst (1, 3, 4, and 5% by weight of used sample) was used in the pyrolysis experiments. Interest is focused on gasoline-rich engine fuel production. The highest yields of gasoline were 53.8% for the gasoline from sunflower oil, which can be obtained from the pyrolysis with 5% catalytic runs. The pyrolysis characteristics of sunflower oil can be explained according to its chemical compositions. The liquid fuel produced from the catalytic pyrolysis has similar chemical components to petroleum-based gasoline.