Brown's first talks with the Roman Catholic leader since he became prime minister in June 2007, will take place on Thursday. Brown met the pope twice as finance minister.
"I'm in no doubt they will want to discuss in particular many of the development issues which is what they've talked about before," said the spokesman.
Brown often mentions his "moral compass" as the son of a Church of Scotland minister. His predecessor Tony Blair, who shied away from discussing religion while in power, converted to Catholicism after leaving Downing Street.
In Rome, Brown will also meet his Italian counterpart Silvio Berlusconi, focusing on the agendas of the Group of Seven nations, which Italy currently chairs, and the Group of 20 countries, currently headed by Britain.
On Wednesday Brown will meet the heads of the World Bank and the International Monetary Fund, Robert Zoellick and Dominique Strauss-Kahn, as part of preparations for a G20 summit in London on April 2.
At the weekend Brown will travel to Berlin for talks with fellow European Union leaders.
"We will be setting out further detail of our proposals for the issues that should be discussed and considered at the G20, and the prime minister is likely to be doing that later this week," said the spokesman.
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