President Cyril Ramaphosa has described Zindzi Mandela as a "fearless political activist who was a leader in her own right".
"Zindzi Mandela was a household name nationally and internationally, who during our years of struggle, brought home the inhumanity of the apartheid system and the unshakeable resolve of our fight for freedom. After our liberation, she became an icon of the task we began of transforming our society and stepping into spaces and opportunities that had been denied to generations of South Africans.
"Her spirit joins Tata Madiba and Mama Winnie in a reunion of leaders to whom we owe our freedom."
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Zindzi Mandela, who was South Africa's ambassador to Denmark from 2015, died in the early hours of Monday morning in a Johannesburg hospital. She was 59.
Minister of International Relations and Cooperation Naledi Pandor earlier said her department was still gathering information on the ambassador's death.
Ramaphosa said Mandela was designated to become South Africa's head of mission in Monrovia, Liberia.
According to the Presidency, Mandela - who was raised in Soweto and educated in SA and Swaziland - spent many years involved in the struggle against apartheid and "embraced roles in the arts, philanthropy and business".
She served as the deputy president of the Soweto Youth Congress, was a member of the Release Mandela Campaign and was an underground operative of Umkhonto we Sizwe.