Adolph became Duke of Nassau on 20 August/30 August 1839, after the death of his father. He supported the Austrian Empire in the Austro-Prussian War of 1866. After Austria's defeat, Nassau was annexed to the Kingdom of Prussia and he lost his throne on 20 September 1866.
In 1879, Adolphe's niece Emma of Waldeck and Pyrmont, the daughter of another of his half-sisters, married her distant relative King William III of the Netherlands. In 1890, their only daughter Wilhelmina succeeded on his death without surviving male issue to the Dutch throne, but was excluded from the succession to Luxembourg by the Salic Law. The Grand Duchy, which had been linked to the Netherlands since 1815, passed to the Dutch royal family's distant relative - the dispossessed Duke Adolphe - on 23 November 1890, in accordance with the Nassau family compact. The Grand Dukes of Luxembourg are still descendants of Adolphe, although through female lines, since the actual independence of the Grand-Duchy required an alteration of the succession laws at the absence of male heirs.
On 23 April 1851, he remarried in DessauPrincess Adelheid-Marie of Anhalt-Dessau (Dessau, 25 December 1833 - Schloss Königstein, 24 November 1916), a daughter of Friedrich, Prince of Anhalt-Dessau. They had five children, of whom only two lived to the age of eighteen and to become prince and princess of Luxembourg:
In 1892, Grand Duke Adolphe conferred the hereditary title Count of Wisborg on his Swedish nephew, Oscar, who had lost his Swedish titles after marrying without his father's approval. Wisborg (also spelt Visborg) was the old castle in the citry of Visby within Prince Oscar's lost Dukedom of Gotland, but the title itself was created in the nobiliy of Luxembourg.