He was the eldest son of Albert IV, Prince of Anhalt-Köthen, by his first wife Elisabeth, daughter of Gebhard III, Count of Mansfeld.
After the death of his father in 1423, Adolph succeeded him in Anhalt-Köthen with his second brother Waldemar V as co-ruler; their younger half-brother Albert VI, still a minor, was bypassed.
Since it appeared as though Adolph's family line would die out in the next generation, he drew up a succession contract with his cousin George I, Prince of Anhalt-Dessau, in 1471.
Thirty-five years later, in 1508, the only two surviving males of the family, Magnus and Adolph, formally renounced their rights over the principality with the result that the Anhalt-Köthen line became extinct.
In Ruppin on 2 November 1442 Adolph married Cordula (died 1 June 1508), daughter of Albert III, Count of Lindau-Ruppin.