As the important part of expressway, the construction technology of asphalt pavement will contribute to the production of greenhouse gases and other volatile organic compounds (VOCs), which has a significant impact on the environment. In order to further analyze the composition, distribution and release of VOCs during asphalt pavement construction, the VOCs emission during paving and rolling were measured through field investigation and sampling. The results show that there are approximately 100 kinds of VOCs substances detected due to the complex organic component of asphalt binder, which is a critical factor to influence the VOCs emission during asphalt pavement construction. During the paving process, the largest VOCs release is 1015.05 ug/m3. With the increase of rolling times, the pavement temperature gradually decrease, and the VOCs emission drops to 266.73 ug/m3. The content of the 10 kinds of substances with the highest concentration accounts for more than 50% of the total VOCs content, in which the proportion of aliphatic hydrocarbons (ALH) and oxygenated hydrocarbon (O-HYD) of the paving process are the highest, while the proportion of aromatic hydrocarbons (ARH) is dominated in the rolling process. The results are vulnerable to the external environment, especially at lower emission level. The relevant research results have certain guiding significance for the control and treatment of harmful gas emission in the construction process of asphalt pavement.