The memorandum of understanding with Houston-based Axiom Space sets out plans for a flight that would see British astronauts conduct a two-week mission in space.
"On this future flight, the UK astronauts would launch to space, spending up to two weeks on orbit to carry out scientific research, demonstrate new technologies, and participate in education and outreach activities," the agency said.
Axiom was founded by its chief executive Michael Suffredini, who served as NASA's International Space Station (ISS) program manager from 2005 to 2015.
It has sent two crewed missions into orbit with SpaceX rockets in April 2022 and in May this year.
The first mission carried an astronaut and three "investors" with the crew spending 17 days in orbit.
The second mission carried a crew of four and lasted 10 days.
Axiom says it is working on what will become the first-ever commercial space station.
The mission with the UK would be commercially sponsored and supported by the European Space Agency.
It would build on the UK government's space strategy which identifies five technologies as critical: artificial intelligence, engineering biology, telecommunications, semiconductors and quantum technologies.
"With this agreement as the initial foundation, we will build a comprehensive mission plan in support of the UK's national and agency objectives to advance its capabilities in space exploration and discovery," Suffredini said.
Helen Sharman from Sheffield became the first Briton in space in 1991 when she went into orbit aboard a Soviet Soyuz TM-12 space capsule.
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