The Blackhawks also received a second-round pick in the 2023 Upper Deck NHL Draft and a fourth-round selection in the 2026 NHL Draft for future considerations.
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Zaitsev, a 31-year-old defenseman, had five assists in 28 games for Ottawa this season. He has 108 points (19 goals, 89 assists) in 426 regular-season games with the Senators and Toronto Maple Leafs, and two assists in 18 Stanley Cup Playoff games.
"We are getting an NHL-caliber defenseman and acquiring very valuable draft capital in this upcoming draft and beyond," Chicago general manager Kyle Davidson said. "Nikita gives us added depth on the right side and we anticipate him joining us soon."
Ottawa acquired Zaitsev in a trade from Toronto on July 1, 2019. He has one more season remaining on the seven-year, $31.5 million contract ($4.5 million average annual value) he signed with the Maple Leafs on May 2, 2017.
"I remember when he first came in the League (in 2016-17), I saw him more in Toronto than Ottawa, I liked him," Chicago coach Luke Richardson said after a 4-3 win at the Dallas Stars on Wednesday. "I thought he played feisty and he moves the puck. Reliable. Always great to have reliable defenseman around.
"I think some of our people here have heard from Ottawa and said he's a great guy, everybody enjoys him, he gets along with everybody. [He] speaks English well, so it should be an easy transition."
NHL.com independent correspondent Taylor Baird contributed to this report