In 1614 he was elected Member of Parliament for Wootton Bassett in the Addled Parliament. He was elected as M.P. for Chippenham in 1621 and for Wiltshire in 1624. He was a Deputy Lieutenant for Wiltshire in 1624. In 1625 he was created a Knight of the Bath. He was elected MP for Cricklade in 1628 and sat until 1629 when King Charles I decided to rule without parliament for eleven years. He was Sheriff of Wiltshire in 1631. In April 1640, Hungerford was elected MP for Chippenham in the Short Parliament. He was re-elected MP for Chippenham for the Long Parliament in November 1640. At the outbreak of the Civil War he took the side of Parliament, and on 11 July 1642 was sent to execute the militia ordinance in Wiltshire. He was excluded from pardon in the king's declaration of grace to the inhabitants of Wiltshire of 2 November 1642, and having been put in command of the Wiltshire forces, made Devizes his headquarters. In December 1642 he attacked Lord Cottington at Fonthill, threatening to bring his troops into Fonthill House, where Lord Cottington lay sick, unless he paid £1,000 to Parliament. Against such treatment Lord Cottington appealed to Parliament, and the Speaker desired Sir Edward to desist. In January 1643 Hungerford had a violent quarrel with Sir Edward Baynton, the parliamentarian governor of Malmesbury, each accusing the other of intended treachery. In February 1643 he occupied and plundered the city of Salisbury, but finding himself unsupported by the county, evacuated Devizes and retired to the city ofBath. When Waller recaptured Malmesbury for Parliament he appointed Hungerford governor, but while Hungerford was still at Bath seeking supplies, Malmesbury was abandoned by the officer whom he had nominated to represent him. Hungerford published a 'Vindication' of his conduct, dated at Bath 28 April 1643. After taking part with Sir William Waller in the Battle of Lansdowne and Battle of Roundway Down, Hungerford besieged Lady Arundel in Wardour Castle, Wiltshire. He treated the lady with little grace, carrying her with scant ceremony to Hatch and thence to Shaftesbury, and keeping her all the while "without a bed to lie on". Subsequently, Hungerford attacked Farleigh Castle, which was garrisoned for the king and under the command of Colonel John Hungerford, said to have been Sir Edward's half-brother. The castle surrendered to Sir Edward in September 1645. He had a reversionary right to the property under the will of Sir Edward Hungerford, his maternal uncle, but the testator's widow had a life-interest, and remained there until 1653.
Marriage
In 1620 he married Margaret Holliday, a daughter and coheiress of William Holliday, an Alderman of the City of London. The marriage was childless. She survived him until 1672, when she was also buried at Farleigh.
Death and burial
Hungerford died in 1648 and was buried in St Anne's Chapel, the north transept chapel of St Leonard's Chapel within the walls of Farleigh Castle. His magnificent tomb chest, with effigies of himself and his wife, survives.
Succession
His will was proved on 26 October 1648. In 1653 his widow Margaret petitioned the Council of State to pay her £500, a small part of the sum borrowed from her husband by Parliament. Parliament had ordered repayment in 1649. Oliver Cromwell appears to have interested himself in her case. Sir Edward's reversionary interest in the Farleigh estates passed to his royalist half-brother Anthony Hungerford.