"If the new president of Libya asked you to open a store in Tripoli, would you consider it?" Clinton asked Wal-Mart CEO Mike Duke at the opening session of the Clinton Global Initiative.
The annual forum brings together leaders in politics, business and philanthropy for three days of brainstorming about the most pressing global problems.
Duke was on a Clinton-mediated panel with U.N. Secretary-General Ban Ki-moon, Queen Rania of Jordan and World Bank President Jim Yong Kim.
The Wal-Mart executive — jokingly calling the corporate giant a "small company from Arkansas," Clinton's home state — said the company already operates in high-risk areas including parts of sub-Saharan Africa. But Wal-Mart has no presence in Tripoli, the Libyan capital Clinton named as a possible location.
Newly elected Libyan President Mohammed el-Megarif is listed among about 1,000 forum participants, as is Egyptian President Mohammed Morsi, a leader of the Islamist Muslim Brotherhood.
Libya faces more domestic upheaval after the killings of U.S. Ambassador Christopher Stevens and three other Americans in the Libyan city of Benghazi earlier this month. Both Egypt and Libya have seen protests against an anti-Islam film made in the United States that denigrates the Prophet Muhammad.
More than 50 current or former heads of state are lined up for this year's high-power gathering. On Sunday, the audience in the ballroom of the Sheraton New York Hotel included the former president's daughter, Chelsea Clinton.
Secretary of State Hillary Rodham Clinton is to speak on Monday morning, and President Barack Obama and Republican presidential candidate Mitt Romney on Tuesday.
The theme of the 2012 meeting is "Designing for Impact." Its stated purpose is to consider how theClinton Global Initiative community "can utilize our abundance of global capacity to invent better tools, build more effective interventions, and work creatively and collaboratively to design a future worth pursuing."
The U.N. secretary-general said the "top priority" is sustainable development — especially for basic needs such as energy, food and water in poor parts of the world.
"I'm going to sound an alarm to all the leaders," he said. "We are living in an era of insecurity, injustice, inequality and intolerance, and what should we do?"
He called on powerful businesses like Wal-Mart to not only act for profit but also "for humanity."
The World Bank head noted, however, that even effective efforts such as delivering HIV-fighting drugs to impoverished countries with high infection rates cannot succeed unless ways are found to expand help to large numbers of people.
"How do you go from promising initiatives to taking things to scale?" Kim asked.
One solution is to knock down the average cost of a year's HIV treatment so it's more accessible in low-income societies. In four African countries — Ethiopia, Malawi, Rwanda and Zambia — the cost averages about $200, compared with $682 in South Africa, according to research by the Clinton Health Access Initiative.
Since Clinton created the Global Initiative in 2005, members have made 2,100 "commitments" seeking to improve the lives of people in more than 180 countries.
On Sunday, Clinton highlighted a Procter & Gamble-sponsored project aiming to provide 2 billion liters of clean drinking water every year to save the life of one child per hour in the developing world.
But he said the long-term prospects for struggling societies rest on educating workers and helping them land jobs, or run their own businesses, "and at least maximize chances that they'll have something to look forward to when they get up in the morning."