Weeks after switching her allegiances from Australia to Samoa, Pelite had a hand in three tries to kickstart Samoa's Pacific Bowl campaign against their arch-rivals in Suva.
The result means Samoa will face the winner of Cook Islands and Fiji in a direct qualifier for the 2026 World Cup on November 3, with the winner to advance.
For Tonga, their chances of playing in their World Cup since 2008 are now officially over.
Already a gold medallist for Australia in rugby sevens at the 2016 Olympics, Pelite was part of the Jillaroos' World Cup-winning side in 2022.
But after watching Samoa reach the men's final in that tournament, she was inspired to switch her allegiances and represent her Samoan heritage this year.
The Gold Coast star's impact was immediate on Saturday in Suva, aided by several other NRLW players.
She laid the platform for Samoa to score through fellow Titan Sarina Masaga in the first set, when she made a half-break through the middle and put her side on the front foot.
From a quick play-the-ball, the space was then created for Monolisa Soliola to put Masaga over out wide.
Titans lock Sienna Lofipo then made it 12-0 for Samoa, before Filomisa Hanisi put Tonga back in the game by barging through four defenders.
But then Pelite took charge for the Jamie Soward-coached Samoan side.
She sent Jessica Patea over in the 28th minute, before creating the space for Masaga to have her second in the 31th minute.
Pelite eventually finished with 166 metres and five tackle busts, helping prove the difference for Samoa.
Tonga briefly mounted a comeback to get it back to 20-16 early in the second half, before Patea's second and a late Lindsay Tui try got Samoa home.
Newcastle second-rower Evah McEwen was also immense off the bench for the Samoans, while Wests Tigers playmaker Pauline Piliae-Rasabale's kicking game also shone through.
For Tonga, Hanisi was also strong off the bench and Lavinia Tauhalaliku a force on the wing, but they couldn't help their side claim a historic first win over their traditional rivals.
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