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Sio won 74 caps for Australia, starting in the 2015 Rugby World Cup final and also featuring in the 2019 tournament, before switching to Samoa last year.
He helped them qualify for the 2026 World Cup and will aim to follow in the footsteps of his father David, who played for Western Samoa in the 1991 edition.
Sio played 143 times for Brumbies before moving to Exeter in 2022 and has so far made 80 appearances for the Chiefs, including 13 starts this season.
“We had a really open and honest conversation with Scott when we met him and we were really impressed,” said head coach Corniel van Zyl.
“His career to date speaks for itself, 74 Tests for Australia, two for Samoa, over 100 games for Brumbies and 80 for Exeter.
“He is durable, has played at the highest level and is keen to test himself in a new environment and competition.”
Domachowski is moving west while Ed Byrne has already left to return to Leinster on a short-term contract after two injury-hit seasons.
Sio is Cardiff’s second confirmed signing after a deal was confirmed last week for Namibia centre Le Roux Malan from Sharks.
The Blue and Blacks have also agreed new contracts with Wales internationals Josh Adams, Alex Mann, James Botham, Mason Grady, Keiron Assiratti and Southworth.
BBC News
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