"If at any time they would say, hang on, we've reconsidered, we'd like to stay, I would receive them with open arms," Timmermans told a conference in Prague.
"It's entirely up to them," he added less than a week before the Brexit talks are due to start.
Timmermans joined French President Emmanuel Macron, who said Tuesday that the door was always open for Britain to return while the negotiations on Brexit are under way.
Timmermans himself nevertheless added he expected Britain to leave the EU.
"We're anxious to know how they want to leave, that's the process we're in right now and I frankly believe they will continue with that and they will leave," he added.
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