Cross-border e-commerce logistics and transportation system is important link in the cross-border e-commerce supply chain. How to choose a fast, safe, reliable, and low-cost logistics transportation mode is an urgent problem to be solved in cross-border e-commerce logistics. In view of this, this paper first analyzes the system characteristics of cross-border e-commerce logistics transportation systems and analyzes the factors affecting the choice of transportation mode from the perspective of reliability. Then, based on the ELECTRE method system, a multiattribute decision-making method for cross-border e-commerce logistics transportation mode selection is proposed. Finally, through a data example, it is verified that the model constructed in this paper and the proposed multiattribute decision-making method can effectively help cross-border e-commerce choose logistics transportation mode according to goods.