She would have to prove herself over and over during a time when few women got such posts, let along pretty former actresses. But she earned the respect of colleagues and world leaders.
A Republican (she ran unsuccessfully for Congress in 1967), she served in Richard Nixon's administration as a member of the delegation to the United Nations General Assembly. She later served President Gerald Ford as ambassador to Ghana, then as his chief of protocol in 1976 and 1977.
During the administration of Ronald Reagan — her former co-star — she served as a State Department trainer. And in the first Bush administration, she was ambassador to Czechoslovakia during the historic days when the Iron Curtain fell.
"She is like a fresh breeze that has gently blown into our midst," Saudi Arabian Ambassador Jamil Baroody said in 1969. "After I heard her speak, I realized that Shirley Temple has not rested on her laurels as a child movie star. She has emerged as a sincere activist and an exponent of youth and its aspirations."
She had to defend her appointment as ambassador to Ghana after it was announced in 1974.
"There are many of us who should be in a position to bring peace to the world. ... Most of the people in Ghana wouldn't know me as an actress. They'd know me for my work at the U.N.," she said.
The Associated Press reported from Accra, Ghana, in 1975 that the new ambassador discussed the economy in great detail and "startled the embassy pros" by turning up at her desk in a Ghanaian outfit of printed cotton head scarf and gown.
Temple also made a point of saying "welcome" and "thank you" in local languages and "delighted the ladies of the Market Women's Association ... embracing them as sister working girls."
She said she got the posting after Secretary of State Henry Kissinger heard her discussing Namibia at a party and was "surprised that I even knew the word."
"The pose, charm and hard work that made her one of the highest paid stars in Hollywood in her childhood has won Uncle Sam unexpected box office appeal in West Africa," the AP reported at the time.
Returning to Washington in 1976, she was appointed by Ford as U.S. chief of protocol, a job that she described as "a lot of parties for one who doesn't like parties."
In 1989, after Bush took office, Temple was sent to Czechoslovakia as ambassador. A few months after she arrived in Prague, communist rule was overthrown there and across Eastern Europe.
"My main job (initially) was human rights, trying to keep people like future President Vaclav Havel out of jail," she said in a 1999 Associated Press interview.
"Almost overnight, my concern became economics," she said.
She accompanied Havel, the former dissident playwright, when he came to Washington as his country's new president in early 1990.
She considered her background in entertainment an asset to her political career. "Politicians are actors too, don't you think?" she once said. "Usually if you like people and you're outgoing, not a shy little thing, you can do pretty well in politics."
Her work in the Reagan administration had been more low-key. She conducted State Department seminars for ambassadors and their wives. (She and Reagan had acted on screen together in "That Hagen Girl" in 1947.)
Temple said her interest in international work came after her brother George was diagnosed with multiple sclerosis in 1952. She became active in the local and national MS societies and eventually helped found an international federation of MS groups. She said her United Nations service in the late 1960s made her more aware of the needs of the Third World.
"I felt right away that the superpowers always seemed to like talking to each other, and there weren't enough countries talking to the developing countries," she told the AP in 1975.
The Clinton years ended her diplomatic career, though she remained active in groups such as the American Academy of Diplomacy, of which she was a charter member.
In the 1975 interview, she bristled (but with a laugh) at the label "former child star."
"Dr. Kissinger was a former child. Jerry Ford was a former child. Even F.D.R. was a former child. I retired from the movies in 1949, and I'm still a former child."
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