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The death of the jinking winger, who scored 14 tries in 27 appearances for the Springboks including four in a single test, comes just weeks before the World Cup kicks off in Japan. He was due to attend as one of the event's past legends.
His fellow wing James Small, another charismatic member of South Africa's title-winning side of 1995 in which Williams was the only non-white player, died less than two months ago.
Williams' try-scoring exploits, and trademark broad smile, made him an instant hero and gave black South Africans a reason to support the Springboks in the early years of the country's transition away from apartheid.
He had been injured before the World Cup but returned for the quarter-final against Western Samoa, becoming a household name overnight after scoring four tries in a 42-14 win.
Player of the year in South Africa in 1994, Williams' career was plagued by knee injuries that restricted his test appearances.
"The news of Chester’s passing is devastating and hard to believe, as he was still young and seemingly in good health," said SA Rugby president Mark Alexander.
"Chester was a true pioneer in South African rugby and his performances at the World Cup in 1995, as a snapshot of his Springbok career, will forever be etched in the hearts and minds of our rugby public. His influence stretched wider than just the rugby world."
Kobus Wiese, a '95 team mate, paid tribute to "a talented player, an important member of our rugby family, a loving father who adored his children, a man loved by his community."
"As a group our hearts are bleeding and filled with sadness at the loss of our brother," he added
World Rugby chairman Bill Beaumont added on Twitter: "Desperately saddened to hear of Chester Williams’s passing. A symbol of the rainbow nation, Chester’s name will forever epitomise a remarkable and transformational Rugby World Cup 1995. We’ve lost a great, engaging man far too soon."
Williams, married with three children, turned to coaching after his playing days, starting with the South African sevens side that won bronze at the Commonwealth Games in 2002. He worked later in Uganda, Romania and Tunisia.
He was coaching the University of the Western Cape at the time of his death and had recently launched his own beer to coincide with the Rugby World Cup build-up.