China’s outward foreign direct investment (OFDI) and export to the countries along the Belt and Road are growing rapidly. However, little is known about how China’s OFDI and export impacts export technological sophistication of countries along the Belt and Road. Adopting panel data from 62 countries along the Belt and Road between 2003 and 2017, this paper empirically examines how China’s OFDI and export impacts export technological sophistication of the countries along the Belt and Road. This paper finds that China’s export can significantly increase the export technological sophistication of the countries along the Belt and Road. While China’s OFDI and the export technological sophistication of the countries along the Belt and Road are not linked before the Belt and Road initiatives is proposed, both are significantly linked after the Belt and Road Initiatives is proposed. In addition, China’s OFDI plays a major role instead of China’s export. Further research shows that there is a threshold effect between China’s OFDI and export technological sophistication of the countries along the Belt and Road. The impact of OFDI on export technological sophistication shows a U shape with the economic development level of the countries along the Belt and Road.