Distillation is an essential thermo chemical process; it mainly depends on temperature which affects mostly the product yield and composition. The aim of this research is to investigate the effect of temperature on the characterization of bio-oil liquid fraction derived from palm kernel shell (PKS) bio-oil. The temperatures were 100 °C and 140°C. The higher heating value (HHV) obtained were 28.6MJ/Kg and 31.5MJ/Kg for bio-oil fraction 100°C and 140°C respectively. The GC- MS analysis determined that phenol is the dominant product in bio-oil fractions.