The four American men and one woman were met in Qatar by senior US officials and will be flown later to Washington.
Five Americans jailed for years in Iran and widely regarded as hostages are on their way to the United States.
The last pieces in a controversial swap mediated by Qatar fell into place when $6 billion of Iranian funds held in South Korea reached banks in Doha.
It triggered the departure of the four American men and one woman in Tehran, who are also Iranian citizens, on a chartered flight to Qatar's capital.
They were met by senior US officials and will be flown later to Washington.
The US has said its citizens were imprisoned on baseless charges for use as political leverage.
Five Iranians imprisoned in US jails, mainly on charges of violating US sanctions, are also being granted clemency as part of this swap.
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