The objective of this study is to investigate the correlation between the chemical properties of bio-oil form different sources on its road performance of asphalt binder. In this study, the bio-oil from the rapid pyrolysis of corn stalks with different states was chosen to prepare bio-asphalt binder. The SARA Four-component test and Gel Permeation Chromatography test were conducted to analyze the chemical properties of bio-asphalt binder, and the correlation between group components, molecular weight distribution and conventional road performance of bio-asphalt binder was established based on grey relation theory. The results show that the bio-oils mainly increase the content of small molecular components (M<1000) in asphalt binder, decrease the average molecular weight, and improve the polydispersity. The asphaltene content mainly determines the temperature sensitivity of asphalt binder, the resin affects the low-temperature performance indexes such as ductility and brittle point, while the saturation and aromatic mainly affect the viscoelastic properties. The average molecular weight of bioasphalt affects its macro performance, and the polydispersity has a significant effect on the high-temperature stability. Finally, semi-liquid bio-oil, which is the mid-layer product of rapid pyrolysis of corn stalks, is recommended as the reasonable raw material for the preparation of bio-asphalt binder.