The following is a list of ambassadors.
Alpha Centauri (pre-Federation)
Andoria (pre-Federation)
Earth (pre-Federation)
Tellar (pre-Federation)
Vulcan (pre-Federation)
United Federation of Planets
- Alkar, Ves (ambassador-at-large)
- April, Robert (ambassador-at-large)
- Archer, Jonathan (to Andoria, 2169 - 2175)
- Oleet, Titus
- Dax, Curzon (to the Klingon Empire)
- Fox, Robert (to Eminiar VII)
- Gav
- Hawkins (to Mordan IV)
- K'Ehleyr (to the Klingon Empire)
- Kell, Natha
- Krajensky
- Lojal (ambassador-at-large)
- Odan (to the two moons of Peliar Zel)
- Talbot, St. John (to Nimbus III)
- Taxco
- Troi, Lwaxana
- Sarahd
- Sarek
- Shras
- Spock (special envoy to Qo'noS, 2293, later ambassador plenipotentiary)
- Taxco (ambassador-at-large)
- T'Jan
- T'Pel (to Romulan Star Empire
- Vadosia
- Vanderbilt, Thomas
- Worf (to the Klingon Empire)
Klingon Empire
- Kell
- Kor (to Vulcan)
- Korrd (to Nimbus III)
- Klingon ambassador (to Federation)
Romulan Star Empire
- Caithlin Dar (to Nimbus III)
- Nanclus (to the Federation)
Other
- Briam (Krios to Valt Minor)
- Byleth (Iyaaran to Federation)
- E'Tyshra (T'Lani III)
- Falow (Wadi to Federation)
- Hodin (Gideon to Federation)
- Kollos (Medusan to Federation)
- Loquel (Iyaaran to Federation)
- Mauric (Kes to Federation)
- O'Zaal (co-coordinator of the Antarian Trans-stellar Rally)
- Petri (Troyius to Elas)
- Riva (Ramatis III)
- Sharat (Kellerun)
- Voval (Iyaaran to Federation)
Unnamed Ambassadors
- Catullan Ambassador
- Klingon Ambassador
- Tholian ambassador(s)