The foreign policy chief, 42, is said to be looking to soften the tone of global relations after Britain became involved in wars in Iraq and Afghanistan, the Associated Press reports.
"He will meet Angelina Jolie in New York for talks," said a spokeswoman for Miliband.
Jolie, 32, a goodwill ambassador for the United Nations High Commissioner for Refugees, is also due to appear on a revamped Web site for the Foreign Office.
The youthful Miliband, the son of WWII Holocaust survivors, was Britain's first blogging Cabinet minister in his former position as environment chief. He also plans to launch a new blog on Wednesday and is encouraging key aides to follow his example.
"The day when we communicated mainly by telegram [is] over," Miliband told the Evening Standard newspaper. "Communication has to be for the masses now, not just elites."
Who's turning 40? Which celebs are high school dropouts? What's hot and definitely not in fall fashion? Check out PEOPLE's new digital magazine now!
JOSH & FERGIE: ROCKED BY SCANDAL
Did he cheat with a stripper?
Married less than a year, the couple denies an Atlanta woman’s claims that she and Josh had a fling
Note that this week’s cover of PEOPLE may differ regionally
