The Elector and Archbishop of Cologne, Archduke Maximilian Franz of Austria, who had been exiled in the Second World War, stayed in the palace in 1814, and the Queen of Naples and Sicily, Maria Carolina of Austria, who suffered the same fate. In 1805 and 1809, French occupation troops were quartered there. Under Emperor Franz I of Austria, splendid summer festivals took place in the palace park.

After the death of Emperor Franz in 1835, the palace served primarily as an imperial guesthouse. Between 1839 and 1841, the Southern Railway, running along a high embankment 400 meters east of the palace, was built. In October of the revolutionary year of 1848, the palace served as the headquarters of Field Marshal Alfred Prince Windischgraetz during the reconquest of Vienna by the Imperial forces.

Prominent guests later included the Hungarian Prime Minister Count Gyula Andrássy, the German Crown Prince couple Friedrich Wilhelm and Victoria (1873) and Nāser ad-Din Schāh, Shah of Persia during his visit to the Vienna World Exhibition in 1873. On June 6, 1867, the 18-year-old Archduchess Mathilde, youngest daughter of Archduke Albrecht of Austria-Teschen, died here after a serious fire accident.

The tram has run along Hetzendorfer Straße since 1907. From 1912 to 1914, with the approval of Emperor Franz Joseph I, Archduke Karl, Austria's last monarch from 1916, lived with his family in Hetzendorf Castle.

During the Austro-Hungarian Empire, the palace was administered by the Imperial and Royal Palace Administration of Schönbrunn and Hetzendorf and the Imperial and Royal Court Garden Administration of Schönbrunn and Hetzendorf. It was part of the Court Office. At the beginning of November 1918, the new state of German Austria effectively assumed control of these two offices. In 1919, the Court Office was formally taken over by the Republic under the Habsburg Law. The two administrative institutions became federal offices in 1920.

The sculptor Anton Hanak lived here from 1923 until his death in 1934; another tenant during the interwar period was the violin virtuoso Bronisław Huberman.

Despite a bomb hit at the end of World War II – which affected the left wing of the Court of Honor – a large part of the precious Baroque interior survived. It had been stored in salt mines in time. In 1946, the City of Vienna leased the palace from the federal government for its fashion school and purchased it in 1987.

In 2025, the historic Hetzendorf Castle will become the vibrant setting for Austria's most energetic yoga festival! This iconic baroque castle will host the Yoga Junkies Festival , bringing together a community of wellness enthusiasts for an unforgettable weekend of dynamic yoga sessions, inspiring workshops, and a celebration of movement, music, and mindfulness.