Kiwi pair Michael Venus and Marcus Daniell will face one of the most accomplished doubles players in tennis history first up at the Rio Olympics.

The New Zealanders have drawn Canadian pair Daniel Nestor and Vasek Pospisil, an unfortunate outcome given their opponents' respective world rankings of ninth and 17th.

Venus is ranked 41st and Daniell 58th and while their form on the ATP Tour has been sound, they rarely play together so have spent an intense week in Rio honing their partnership.

In January, 43-year-old Nestor became the first player to win 1000 ATP doubles matches. He has claimed 90 titles with 11 different partners and snared eight grand slam crowns and a gold medal at the 2000 Sydney Olympics.

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Both Daniell and Venus have said they plan to march at the Games Opening Ceremony on Friday, the night before their competition is due to begin.