Through analyzing the value of the activities in the process of express delivery, the model of logistics value chain analysis (LVCA) of express enterprises is constructed. Using the model, the express enterprises can identify the key activities from the whole process of express delivery from senders to receivers, and those key activities constitute the logistics competitiveness of express enterprises. Then a model of logistics competitiveness is established, which includes four aspects: strategic location, network optimization, value-added services and performance measures. Those four aspects form the core logistics competitiveness for express enterprises.