On 20 March 1842 in Munich, Adelgunde married
Archduke Francis of Austria-Este (1819–75), eldest son of
Francis IV, Duke of Modena and
Maria Beatrice of Savoy.
The couple had only one child, Princess Anna Beatrice Theresia Maria (October 19, 1848 in
Gries,
Bolzano – July 8, 1849 in
Modena). Francis acceded to the dukedom on his father's death in 1846 as Francis V. After the
Italian Unification, Francis was deposed, and he and his wife were exiled to Vienna, where he died fifteen years later.