In order to treat waste during oleic acid production, pyrolysis method was used to investigate the plant oil asphalt (POA) to obtain bio-fuel. It was found that the compounds contained alkane, alkene, fatty acid, plant sterol derivatives, alcohol and etc. in pyrolysis products of POA by Pyrolysis-Gas Chromatography-Mass Spectrometer (Py-GC-MS). The Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI FT-ICR-MS) results showed that dehydrogenation and polymerization reactions took place during the pyrolysis process, but the main reaction was decarboxylation. According to van Krevelen diagram the nature of the bio-fuel can be evaluated. The acid value and viscosity of the resulting bio-fuel produced were higher than that of diesel fuel and reference bio-fuel. The calorific value showed a slight lower value than that of diesel oil. These studies nominated POA as a potential renewable feedstock for bio-fuel production the simple pyrolysis method.