The position was established in a de-facto sense with Guo Songtao's appointment as Minister to France (as well as concurrently with the UK) from 1877 through 1879 as part of the United Kingdom's demands after the Margary Affair for an Imperial commissioner to be posted to Britain.

A Victorian photograph of Walter Goodman's 1877 portrait of Guo Songtao.

Qing dynasty

• Guo Songtao (22 February - 25 August, 1878)
• Zeng Jize (25 August 1878 - 28 April 1884)
• Xu Jingcheng (1884?4?28? - ?) - did not take office
• Li Fengbao (1884 - August 23, 1884)
• Xu Jingcheng (1884 - 1887)
• Liu Ruifen (1887 - 1890)
• Chen Qinming (1890) - did not take office
• Xue Fucheng (1889 - 1894)
• Gong Zhaoyuan (1893 - 1894)
• Qingchang (1895)
• Yu Geng () (1899 - 1902)
• Sun Baoqi (2002 - 2005)
• Liu Shixun (1905-1911)
• Dai Chenlin (20 December - 1912)

Republic of China (Minister Beiyang government)

• Dai Chenlin (former Qing minister)
  • Lin Tongshi (22 August 1912 - 2013) (second counselor)
• Hu Weide (November 22, 1912 - April 11, 1919)
• Yue Zhaoxue
• Chen Lu
• Qi Qi
• Gao Lu
• Qian Yongming
• Xie Weilin
• Wellington Koo

Republic of China (Ambassador for Nationalist government in Nanjing)

• Wellington Koo (1936-1941) - resumes post from previous government
• Wei Daoming (1941-1942)
• Guo Zefan (1941-1943)
• Qian Tai (1944-1944)
• Duan Maolan (1949-1956)
• Chen Xiongfei (1956-1963)
• Gao Shiming (1963-1964)

People's Republic of China (1964-present)

Despite the PRC's founding in 1949, France did not begin recognition until 1964 under Charles De Gaulle

• Song Zhiguang (1964-1964)
• Huang Zhen (1964-1971)
• Zeng Tao (1973-1977)
• Han Kehua (1977-1980)
• Yao Guang (1980-1982)
• Cao Keqiang (1983-1986)
• Zhou Jue (1986-1986)
• Cai Fangbai (1990-1998)
• Wu Jianmin (1998-2003)
• Zhou Jinjun (2003-2008)
• Kong Quan (2008-2013)
• Lu Shaye (June 2019-present)