He said Mr Moore, an IT consultant from Lincoln who was seized in Baghdad in May 2007, was in good health and "absolutely delighted at his release".
Mr Miliband said the Moore family felt deep relief after two-and-a-half years of "misery, fear and uncertainty".
Four bodyguards were seized with Mr Moore. Three were shot dead; the fourth is also thought to have been killed.
The bodies of Jason Swindlehurst, from Skelmersdale, Lancashire, and Jason Creswell, of Glasgow, were returned to the UK in June 2009, followed by that of Alec MacLachlan, of Llanelli, Carmarthenshire, in September.
Mr Miliband has called for the release of the body of the fourth guard - Alan McMenemy from Glasgow.
Mr Miliband said Mr Moore, who had been released on Wednesday morning, was in the British Embassy in Baghdad and would be reunited with his family as soon as possible.
We are so relieved and we just want to get him home, back now to his family and friends
Graeme Moore, father
The foreign secretary said he had had a "very moving" conversation with Mr Moore, who was "to put it mildly, absolutely delighted". He is undergoing medical checks.
Mr Miliband said: "The joy and relief that will be felt by Peter's family will be mirrored by the continuing anguish of the family of Alan McMenemy, the last of the five men taken hostage.
"We have believed for some time that he has been killed and his family have been told our view of his likely fate."
The foreign secretary also told the BBC there were no concessions or deals made to secure Mr Moore's release.
"This was an Iraqi-led process of political reconciliation in which an armed group has made vows to come within the political system and to renounce violence, and that's the foundation of Peter Moore's release," he said.
Mr Moore had been working for US management consultancy Bearingpoint in Iraq. The other men were security contractors employed to guard him.
British hostage released in Iraq
The group was captured at the Iraqi Ministry of Finance by about 40 men disguised as Iraqi policemen.
They were understood to belong to an obscure militia known as the Islamic Shia Resistance, which demanded the release of up to nine of their associates held in US military custody since early 2007.
'I'm breaking down'
Prime Minister Gordon Brown said: "I am hugely relieved by the wonderful news that Peter has been freed.
"At this moment of celebration, we also remember the families of British hostages who have been killed in Iraq and elsewhere.
"And we pledge to continue to do everything we can to bring British hostages back to their loved ones."
Mr Moore's father Graeme, 60, from Wigston, Leicestershire, said he was "over the moon" at the news.
Alan McMenemy is believed to have been killed by his captors
He said: "We are so relieved and we just want to get him home, back now to his family and friends.
"I'm breaking down, I'm just so overjoyed for the lad."
Terry Waite, who himself was a former hostage, said he was absolutely delighted at Mr Moore's release.
He added: "It is both a very happy time for Peter and his family and... while the other families will be delighted for him, there will be that tinge of sadness and one keeps them in mind at this point."
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