The swap included executives of Citgo Petroleum held for years, as well as US Marine veteran Matthew Heath and another US citizen named Osman Khan. They were exchanged for two of Maduro's wife's nephews, who were arrested in 2015.
President Joe Biden said the "wrongfully detained" Americans would soon be reunited with their relatives.
"Today, we celebrate that seven families will be whole once more. To all the families who are still suffering and separated from their loved ones who are wrongfully detained - know that we remain dedicated to securing their release," Biden said in a statement.
The prisoner transfer, which one US official said took place at an airport in an unspecified third country, followed months of secretive talks with Maduro's socialist government, which is under strict US sanctions, including on the OPEC nation's energy sector.
It came at a time when Washington is under growing pressure to do more to secure freedom for dozens of Americans held abroad. Much of the Biden administration's focus has been on Russia's detention of WNBA star Brittney Griner and another American, Paul Whelan.
Maduro's government said that as a result of talks that started in March two young Venezuelans "unjustly" held in the United States were freed, as well as a group of US citizens who were subject to Venezuelan court proceedings and were released for "humanitarian reasons".
Biden approved the exchange weeks ago, making a "tough decision, a painful decision" that the release of the two Venezuelans was essential to securing the Americans' freedom. US officials have previously said in private that Maduro wanted to use the detainees as bargaining chips.
The five employees of Houston-based Citgo, who had been detained in Venezuela in 2017, were Tomeu Vadell, Jose Luis Zambrano, Alirio Zambrano, Jorge Toledo and Jose Pereira.
Also released was Heath, a former Marine. He had been held since 2020 on terrorism charges, which he denied.
Khan was identified as a Florida man who had been arrested in January.
In return, the Unites States freed two of Venezuelan first lady Cilia Flores' nephews, Franqui Flores and Efrain Antonio Campo Flores.
The two, arrested in Haiti in 2015 in a US sting operation, were convicted in 2016 on US charges that they tried to carry out a multimillion-dollar cocaine deal. They were each sentenced in 2017 to 18 years in prison.
Citgo welcomed the news that the executives were free, saying in a statement it was "grateful to the leaders in Washington who helped bring about their release".
A Venezuelan court in 2020 sentenced the executives, accused of embezzlement, money laundering and conspiracy, to prison terms ranging from eight to 13 years. They and the company maintained their innocence, and the US State Department called the charges "specious".
