Moon Jae-in told a pre-Opening Ceremony reception on Friday that the games were an opportunity to build peace on the peninsula. Dozens of South Koreans at the airport tried to snap photographs of her on their mobile phones.
North Korea's KCNA new agency announced the following day that it had no intention of meeting U.S. officials during the Games, after which Pence said that the United States expected the recent rapprochement between the two Koreas to end once the Olympic Games are over.
Pictures show the dictator's sister and her delegation being greeting by government officials, including Unification Minister Cho Myong-gyon, before boarding a bullet train to Pyeonchang.
She is believed to be carrying a personal message from her brother to the South's president.
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Speed skater Nao Kodaira, who serves as Japan's team captain for the Pyeongchang Winter Olympics, will not attend the opening ceremony on Friday, her coach Masahiro Yuki said.
"Today's parade demonstrates the power of the Democratic People's Republic of Korea, which has reached the level of the world-class military powers", the North Korean leader said.
But a spokesman for the South's presidential Blue House said he arrived late, "exchanged greetings with those seated at the head table, and left without sitting down".
News reports said 4,000 of the phones were being given to athletes attending the Pyeongchang Games, but that athletes from Iran and North Korea would be excluded because of global sanctions against the two countries.
Nearly 500 North Koreans are participating in the Olympics, in an extraordinary gesture towards peace, while tension over the North nuclear program continues to simmer in the region and around the world.
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While the Vice President has cautioned against cozying up to North Korea, he avoided public criticism of Moon and congratulated South Korea on hosting the Games.
Also likely important: making sure Mr. Pence and Ms. Kim are seated such that "they're not in the same camera frame", he said.
Mr Pence had told Seoul in advance that he would be dining with U.S. athletes soon afterwards "so his seat was not prepared accordingly", the spokesman said.
Pence made a brief appearance and left early to meet with US athletes prior to the Opening ceremony, South Korean officials told Reuters.
Alarm at this turn of events may have inspired Japanese Prime Minister Shinzo Abe to accept the invitation from President Moon to attend the opening ceremony of the Olympics, despite the current diplomatic spat between the two countries over the historical issues of "comfort women" during the Second World War.
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South Korean analysts have nicknamed him "Tape Recorder", he added, "as he always parrots what has been said by the supreme leader".