Under the background of “Carbon Peaking and Carbon Neutrality”, aiming at the low recycling rate of express packaging in China, the research data of 308 college students’ families in Hunan Province were used to study the influencing factors of residents’ express packaging recycling behavior. Based on the expanded planned behavior theory, the structural equation model (SEM) was constructed for verification and analysis, while different models were replaced, and the robustness of the results was tested by linear regression. The research showed that the impacts of perceived behavior control and low-carbon self-identity on residents’ express packaging recycling intention were significantly higher than those of recycling attitude and subjective norms. The implementation of garbage classification will significantly positively regulate the relationship between recycling intention and recycling behavior, and the higher the implementation of garbage classification, the more likely the actual behavior of express packaging recycling will occur.