Lee Seo-Hyun will lead management planning at the Everland's fashion business, Samsung said in a statement.
The 40-year-old was previously executive vice president of Cheil Industries, which was the former fashion unit before it handed over operations to Everland.
Her older sister -- Lee Boo-Jin -- has been a president at Everland since 2010, overseeing business strategy, while their only brother, Lee Jae-Yong, was made vice chairman of Samsung Electronics last year.
Lee Kun-Hee is chairman of the group's flagship unit Samsung Electronics and de facto leader of the entire business empire.
The move is the latest promotion in recent years of the three heirs of the founding family, which controls Samsung through a complex web of share cross-holdings in group subsidiaries centred on Everland.
There was no major reshuffle of top executives within Samsung Electronics -- the world's top maker of mobile phones and TVs.
The senior Lee is largely credited with turning Samsung -- founded by his father in 1938 -- into a global brand and the country's largest business group.
He stepped down as the group's chairman in 2008 after being found guilty of tax evasion but returned to the post in 2010 after receiving a presidential pardon.
Samsung has rapidly expanded its presence in the global smartphone market, dethroning Apple as the world's top smartphone maker amid worldwide patent battles against over technology and design.
The South Korean tech giant has a 31.4% stake in the global smartphone market by shipment in the third quarter of this year, compared to 13.1 percent for Apple, according to the research firm IDC Survey.
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