This paper focuses on estimating highway transportation greenhouse gas emission volume and greenhouse gas external cost in China. At first, composition and characteristics of greenhouse gases were analysed about highway transportation emissions. Secondly, an improved model of emission volume was presented on basis of highway transportation energy consumption, which may be calculated by virtue of main affecting factors such as the annual average operation miles of each type of the motor vehicles and the unit consumption level. the model of emission volume was constructed which considered not only the availability of energy consumption statistics of highway transportation but also the greenhouse gas emission factors of various fuel types issued by IPCC. Finally, the external cost estimation model was established about highway transportation greenhouse gas emission which combined emission volume with the unit external cost of CO2 emissions. An example was executed to confirm presented model which ranged from 2011 to 2015 Year in China. The calculated result shows that the highway transportation total emission volume and greenhouse gas external cost are growing up, but the unit turnover external cost is steadily declining. On the whole overall, the situation is still grim about highway transportation greenhouse gas emission, and the green transportation strategy should be put into effect as soon as possible.