The station, in the direction of Nation, is the true terminus of line 6. Due to the single track loop at Charles de Gaulle - Étoile, the trains cannot stop there for long, so instead they depart quickly back round the loop and then wait for an extended period of time at Kléber.
The station opened on 2 October 1900 as a branch of line 1 from Étoile to Trocadéro. On 5 November 1903 this line was extended to Passy and the line from Étoile to Trocadéro and Passy became known as line 2 South as part of a planned ring line around central Paris to be built under or over the boulevards built in place of the demolished Wall of the Farmers-General; this circle is now operated as two lines: 2 and 6. On 14 October 1907 the line from Étoile to Trocadéro, Place d'Italie and Gare du Nord became part of line 5. On 6 October 1942 the section of line 5 from Étoile to Place d'Italie, including Boissière, was transferred to line 6. The Avenue Kléber commemorates Jean Baptiste Kléber (1753–1800), a General in the Revolutionary and Napoleonic Wars, and particularly noted for his leadership in the Egyptian campaign, where he was assassinated.