When Italy entered World War II, on 10 June 1940, Vivaldi, under Captain Giovanni Galati was the flagship of the 14th Destroyer Division, which she formed along with sisterships Leone Pancaldo, Antonio da Noli and Lanzerotto Malocello.

During escort operations in late 1941 and early 1942, Vivaldi often served as flagship for Admiral Amedeo Nomis di Pollone, commander of the Fleet Destroyer Group.

In June 1942 Vivaldi, now under Captain Ignazio Castrogiovanni, participated in an attack against a British convoy to Malta (Operation Harpoon) and, while clashing with the escorting destroyers, received a hit in the engine rooms that started a massive fire and left her dead in the water.

The fire on Vivaldi burned for hours, virtually cutting the ship in two, with the crew in the bow unable to go to the stern and vice versa, but in the end the flames were extinguished and she was towed to port.

On 9 September 1943, following the Italian Armistice, Vivaldi and sistership Da Noli were ordered to sail from Genoa to Civitavecchia, near Rome, where they would embark the king and the government and bring them to La Maddalena, Sardinia, to prevent them from being captured by the German forces, that had launched Operation Achse.

She still carried on for some more hours at a speed of a few knots, while the crew struggled to save the ship; but in the end her badly damaged engines ceased working, and her commanding officer, Captain Francesco Camicia, ordered her scuttled.

Vivaldi sank on 10 September, about 50 miles west of Asinara island, taking down with her Lieutenant Commander Alessandro Cavriani and petty officer Virginio Fasan, who had gone back aboard to speed up her sinking.

Another group was picked up by a British submarine, HMS Sportsman, which brought them to Algeria, and dozens more reached the Balearic Islands (Spain) after spending days at sea in various boats, some of them staying adrift for a week or more.