May and finance minister Philip Hammond are due to meet executives to discuss Brexit and this week's annual budget, which included spending pledges and higher taxes on technology firms. They will both make statements and then take questions.
"It's part of regular engagement we have with business, it's an opportunity for them to ask questions of the PM and, of course, of the Chancellor (Hammond), about anything they may be interested in," May's spokesman said.
"Of course, Brexit may well be raised."
The government has so far not said where the meeting is taking place or who will be attending.
With five months to secure a deal before Britain is due to leave the European Union, business leaders are demanding certainty over the kind of trade terms the divorce will deliver. In particular, they want reassurances that there will be a 21-month transition period after Britain is due to leave the bloc.
If Britain and the European Union fail to strike a withdrawal agreement, there will be no formal transition period to cushion the impact of Brexit.
Earlier on Wednesday, the opposition Labour Party's finance spokesman John McDonnell also briefed businesses on the budget, and said those attending had quickly focused on Brexit during the discussion.
"We're as worried as they are about the uncertainty and the lack of assurance coming from government about a deal," McDonnell told reporters after the meeting.
The Brexit negotiations are currently stalled over a disagreement on a fallback plan to avoid a hard border on the island of Ireland, former focal point for sectarian tensions, if a future trading relationship is not in place in time.
The latest meeting with business leaders follows a conference call the prime minister held with a similar-sized group of business leaders earlier this month. (Reporting By Andrew MacAskill and William James; Editing by Guy Faulconbridge)
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