This paper adopts the trade intensity index, Revealed Comparative Advantage Index and trade complementary index to analyze the trade structure of China and the countries along the Silk Road. By using the stochastic frontier gravity model with the data from 2006~2017, the trade efficiency of China and 15 Silk Road countries, such as ASEAN, South Asia and other countries are investigated. Both the index and model show that there is a huge potential for trade between China and“Maritime Silk Road”countries. The influence of GDP per capita on China’s trade is far smaller than that of other countries, and the geographical distance is negatively related to the volume of commodity trade, while the impact of regional trade agreements and common boundary variables are not so significant. After that, policy suggestions are put forward to improve the trade efficiency between China and the countries along the line.