Upon Napoleon's return from Elba in the Hundred Days, Exelmans was temporarily made a Peer of France, and was placed in command of the II Cavalry Corps, consisting of Major General Strolz's 9th Cavalry Division and Major General Chastel's 10th Cavalry Division. During the Waterloo Campaign, the corps fought in the battles of Ligny and Wavre. In the final operations around Paris, he won distinction on 1 July at the Battle of Rocquencourt, where units under his command isolated and destroyed an advanced Prussian hussar brigade under the command of Colonel von Sohr.