China continues to integrate into the GVC. The traditional trade statistics method counts the gross trade value into the trade flow，resulting in some errors in accounting China’s real export value. This paper uses the world input-output tables and value-added accounting method to calculate and analyze the industrial and country structure of China’s export from 2000 to 2014, studies the industrial structure and country structure of China’s gross export from the added value aspect. The results show that: (1) China’s value-added export of service industries grows faster than manufacturing industries, but China’s value-added export is still dominated by manufacturing industries. (2) China’s industrial structure of value-added exports has been improved in participating in the GVC. (3) As a whole, China’s upstream participation in GVC is rising, while the downstream participation in GVC is declining. (4) The trade ties of China with United States, European Union, and East Asia have declined, while the trade ties with BRIC countries and other countries have risen. The conclusion of this paper provides empirical support for China’s trade industry policy and international economic cooperation.