During the War of the Seventh Coalition, General Georges Mouton commanded the VI Corps at the Battle of Waterloo.

Under the command of Ney, the VI Corps crossed the Rhine near Karlsruhe on the evening of 24–25 September, 1805 at the start of the War of the Third Coalition.

On 2 October, Napoleon's advancing Grande Armée began to wheel to the right, aiming for the Danube River, with Ney's corps on the right as the pivot.

Surprisingly, the badly outnumbered French fended off the enemy all day, before the discouraged Austrians finally retreated.

On 14 October, Ney fought General Johann Sigismund Riesch's small corps at the Battle of Elchingen.

Using General Loison's 2nd Division, supported by Malher, Ney crushed Riesch's troops with heavy losses.

[9] Ney's 17,000 men held off 63,000 Russians in a brilliant rear guard action in the Battle of Guttstadt-Deppen on 5 and 6 June.

[11] The VI Corps was reconstituted for the invasion of Russia and placed under the command of General Laurent de Gouvion Saint-Cyr.

[19] During the Battle of Leipzig, Marmont defended the northern sector against Marshal Gebhard Leberecht von Blücher's Prussian forces.

After bitter fighting on 16 October, the VI Corps was defeated when the Prussians launched a massed cavalry charge.

[28] At the Battle of Fère-Champenoise on 25 March, the VI Corps and other troops proved unable to stop the advance of the Coalition armies.

It went into action with Lagrange's 1,395 troops, Ricard's 726 men, and General Jean-Toussaint Arrighi de Casanova's 1,250 soldiers.

[31] The next day, Napoleon ordered Mouton to march his corps west to a position where it could attack Wellington's British army and attached General Subervie's light cavalry division.

At the same time, General Teste's division was detached from the corps to operate with Marshal Emmanuel de Grouchy's right wing.

[32] On the morning of the 18th at the Battle of Waterloo, Napoleon placed the VI Corps in the second line, with the divisions of Generals Simmer and Jeanin one behind the other just to the west of the Charleroi to Brussels highway.

[34] At about 4:00 PM, General von Bülow gave the order to attack and Lobau found himself outnumbered three-to-one by the Prussians.

[38] Unaware that Napoleon's army was routed at Waterloo, Teste's detached division attacked and captured the hamlet of Bierges on the morning of the 19th during the Battle of Wavre.