| Inaugural date | Official Position (Japanese) | Official Position | Name |
| January 19, 1863 | 領事 | Consul | Max August Scipio von Brandt [de] |
| February 2, 1867 | 代理公使 | Chargé d'affaires | Max August Scipio von Brandt |
| July 20, 1868 | 総領事 | Consul general | Max August Scipio von Brandt |
| January 5, 1869 | 代理公使 | Chargé d'affaires | Max August Scipio von Brandt |
| June 1871 | 代理公使 | Chargé d'affaires | Theodor von Holleben |
| March 30, 1873 | 弁理公使 | Chargé d'affaires | Max August Scipio von Brandt |
| February 1875 | 代理公使 | Chargé d'affaires | Eduard Zappe [de] |
| April 1875 | 代理公使 | Chargé d'affaires | Theodor von Holleben |
| December 3, 1875 | 弁理公使 | Chargé d'affaires | Karl von Eisendecher [de] |
| April 1878 | 代理公使 | Chargé d'affaires | Felix Freiherr von Gutschmid [de] |
| June 14, 1880 | 特命全権公使 | Minister Plenipotentiary | Karl von Eisendecher |
| April 24, 1880 | 特命全権公使 | Minister Plenipotentiary | Otto Graf von Dönhoff [de] |
| March 11, 1886 | 特命全権公使 | Minister Plenipotentiary | Theodor von Holleben |
| December 10, 1892 | 特命全権公使 | Minister Plenipotentiary | Felix Freiherr von Gutschmid |
| March 3, 1897 | 臨時代理公使 | Chargé d'affaires ad interim | Karl Georg von Treuter [de] |
| March 29, 1898 | 特命全権公使 | Minister Plenipotentiary | Kasimir Graf von Leyden [de] |
| May 23, 1900 | 臨時代理公使 | Chargé d'affaires ad interim | Georg von Wedel [de] |
| May 10, 1901 | 特命全権公使 | Minister Plenipotentiary | Emmerich Graf von Arco Valley [de] |
| February 28, 1906 | 臨時代理公使 | Chargé d'affaires ad interim | Friedrich Carl von Erckert [de] |
| May 22, 1906 | 特命全権大使 | Ambassador | Alfons Mumm von Schwarzenstein |
| April 19, 1911 | 特命全権大使 | Ambassador | Arthur Graf Rex [de] |
| August 1914 | | | |
| August 1, 1920 | 代理大使 | Chargé d'affaires | Wilhelm Solf |
| February 26, 1921 | 特命全権大使 | Ambassador | Wilhelm Solf |
| December 16, 1928 | 臨時代理大使 | Chargé d'affaires ad interim | Wilhelm Albrecht von Schoen [de] |
| January 1, 1929 | 特命全権大使 | Ambassador | Ernst Arthur Voretzsch [de] |
| December 1933 | 臨時代理大使 | Chargé d'affaires ad interim | Willy Eduard Noebel [de] |
| December 27, 1933 | 特命全権大使 | Ambassador | Herbert von Dirksen |
| February 1938 | 臨時代理大使 | Chargé d'affaires ad interim | Willy Eduard Noebel |
| April 28, 1938 | 特命全権大使 | Ambassador | Eugen Ott |
| February 4, 1943 | 特命全権大使 | Ambassador | Heinrich Georg Stahmer |
| May 1945 | | | |
| April 28, 1952 | 臨時代理大使 | Chargé d'affaires ad interim | Heinrich Northe [de] |
| May 19, 1955 | 特命全権大使 | Ambassador | Hans Kroll |
| May 13, 1958 | 特命全権大使 | Ambassador | Wilhelm Haas [de] |
| September 10, 1961 | 臨時代理大使 | Chargé d'affaires ad interim | F. van Briessen [de] |
| March 10, 1962 | 特命全権大使 | Ambassador | Herbert Dittmann [de] |
| January 19, 1965 | 臨時代理大使 | Chargé d'affaires ad interim | Walter Boss [de] |
| March 18, 1966 | 特命全権大使 | Ambassador | Franz Krapf [de] |
| March 26, 1971 | 臨時代理大使 | Chargé d'affaires ad interim | Heinrich Rohreke [de] |
| April 5, 1971 | 特命全権大使 | Ambassador | Wilhelm Grewe |
| October 9, 1976 | 臨時代理大使 | Chargé d'affaires ad interim | Hartmut Schulze-Boysen [de] |
| March 23, 1977 | 特命全権大使 | Ambassador | Günter O. Diehl [de] |
| April 20, 1981 | 特命全権大使 | Ambassador | Klaus W. G. Blech [de] |
| July 10, 1984 | 特命全権大使 | Ambassador | Walter Boss |
| October 22, 1986 | 特命全権大使 | Ambassador | Hans-Joachim Hallier [de] |
| September 28, 1990 | 特命全権大使 | Ambassador | Wilhelm Haas [de] |
| July 11, 1994 | 特命全権大使 | Ambassador | Heinrich-Dietrich Dieckmann [de] |
| September 22, 1997 | 特命全権大使 | Ambassador | Frank Elbe [de] |
| September 22, 1999 | 特命全権大使 | Ambassador | Uwe Kästner [de] |
| December 22, 2001 | 特命全権大使 | Ambassador | Henrik Schmiegelow |
| July 1, 2006 | 特命全権大使 | Ambassador | Hans-Joachim Daerr [de] |
| October 21, 2010 | 特命全権大使 | Ambassador | Volker Stanzel [de] |
| April 9, 2014 | 特命全権大使 | Ambassador | Hans Carl von Werthern [de] |
| September 1, 2019 | 特命全権大使 | Ambassador | Ina Lepel [de] |
| September 1, 2021 | 特命全権大使 | Ambassador | Clemens von Goetze [de] |