Joined by singer Wyclef Jean, who was born in the Caribbean country, the star of The Bourne Ultimatum handed out food bags and medicine to those left hungry and homeless after Hurricane Ike crossed the island last week.
The two celebrities are encouraging people to help the United Nations raise more than £55 million for the isle, which has been hit by four devastating tropical storms and hurricanes this year.
"Hopefully, we can make enough noise that people will pay attention," said Matt. "I truly believe in the people of my country."
On Sunday, the duo will take a helicopter to the north of the county to distribute further supplies as well as visit the cathedral, which has become a temporary home for 500 islanders.