Mundy was the third son of Edward Miller Mundy, and grandson of Edward Miller Mundy of Shipley Hall, Derbyshire, England, a Tory politician who represented the seat of South Derbyshire. He enlisted in the army and was in Sydney in November 1827 when he was promoted to Second Lieutenant, 94th Regiment of Foot, later promoted to Lieutenant, 21st Regiment of Foot. He was appointed Magistrate in Tasmania in March 1835. and Justice of the Peace in 1837. He resigned his commission in 1839, but was later commonly referred to as "Lieutenant Mundy". On 11 July 1839 Mundy, John Bourke and Joseph Hawdon set out from Melbourne for Adelaide, Mundy and Bourke on a light tandem and Hawdon on horseback, following the route taken by Charles Bonney via Portland Bay and the Glenelg River. They arrived in Adelaide exactly a month later, and estimated it could easily be done in half that time. He joined with Edward Bate Scott and Edward John Eyre, who had a scheme to purchase and transport livestock from Adelaide to the Swan River Colony, aboard chartered ships as far as King George's Sound and then drive them overland to Perth. On 30 January 1840 they loaded some stock onto the schooner Minerva and a few days later the remainder onto the barque Cleveland. Eyre sailed aboard Minerva while Mundy was aboard the Cleveland. The stock consisted of 1700 sheep, which included over 1000 ewes and 450 lambs, 6 horses and 100 cattle. They achieved good prices in Perth, and would have made a tidy profit except many sheep and cattle died on the track in Western Australia, ascribed to their eating poisonous plants. On 3 April 1840 Eyre and Mundy were elected honorary members of the W.A. Agricultural Society. They arrived back in Adelaide aboard Minerva in May 1840. Mundy was appointed acting Clerk of Council in June 1840 and Private Secretary to the newly appointed Governor Grey in May 1841. He was appointed by the Governor to the Legislative Council 15 June 1843, originally as a non-official appointee, then as Colonial Secretary from 15 June 1848 to 14 June 1849 when he returned to England on leave of absence. His brother Edward Miller Mundy, M.P. for South Derbyshire, had died on 29 January 1849 and Alfred resigned on succeeding to the family estates, which included lucrative coal mines. He was High Sheriff of Derbyshire in 1855, and a J.P. and D.L. for that county and a J.P. for Nottinghamshire. He died while on holiday in Nice.
Family
Alfred Miller Mundy married Jane Hindmarsh on 5 June 1841. She was the eldest daughter of John Hindmarsh.
Nelly Hindmarsh Miller Mundy married Charles John Addington in 1862.
Alfred Edward Miller Mundy married Ellen Mary Palmer-Morewood of Alfreton Hall fame. She deserted him for the young Charles John Chetwynd-Talbot, Earl of Shrewsbury. They divorced in 1881 and she later became Lady Shrewsbury.
He inherited the estate of his older brother Edward Miller Mundy, M.P. for Derbyshire Sir Robert Miller Mundy KCMG, Lieutenant-Governor of Grenada, was another brother.