Palombini became "chief of brigade" (colonel) of the 2nd Hussar Regiment on 23 February 1804 and went to command the unit at the Camp of Boulogne. This regiment later became the "Napoleone" Dragoons. On 28 August 1806 he married Carolina Amalia Beatrice Dąbrowski, the daughter of the Polish general Jan Henryk Dąbrowski. He was appointed a knight of the Order of the Iron Crown in 1806, and at a later date, a commander of the order. He was part of the Italian contingent sent to Germany to fight in the War of the Fourth Coalition. The "Napoleone" and "Regina" Dragoons fought at the Siege of Kolberg which lasted from 20 March to 2 July 1807. The commander of the Italian division, Pietro Teulié was killed during the unsuccessful siege. In July, the division marched to participate in the Siege of Stralsund which had begun on 15 January 1807. With the division under Pino's leadership, the two dragoon regiments joined the besieging force until 20 August when the Swedes evacuated Stralsund.