Scheffler, who won the Masters in April, booked his spot in the Davis Love III-captained American team on Sunday, with the automatic qualifiers for both teams being finalised after the BMW Championship.
Patrick Cantlay, Xander Schauffele, Justin Thomas and Tony Finau are among the players in the American team with prior experience of the Presidents Cup, a biennial event that pits a 12-man team from the US against international players from outside Europe.
Sam Burns was the only other rookie to make it onto the US team for the September 22-25 tournament at Quail Hollow in Charlotte, North Carolina.
"In 2022, we've seen (Scheffler's) true potential shine as he's ascended to the number one player in the world, but also has cemented himself as a guy who has earned the respect of his peers and teammates," Love said.
"This will certainly be the first of many Presidents Cups for him."
Internationals captain Trevor Immelman could be without Australian world number two Smith, who has consistently been linked in media reports with a switch to the LIV Series since he won last month's British Open.
A report in Britain's Telegraph on Saturday said the Australian was one of seven new player signings set to be announced by the Saudi-backed tour. The report added that he is expected to play at LIV's event in Boston in September.
Players participating in LIV Golf events have been suspended by the PGA Tour, which owns the Presidents Cup.
Australian Adam Scott and Japan's Hideki Matsuyama will be making their 10th and fifth appearances in the tournament respectively.
"We've got a hard task every time we go out to beat an American team that's just stacked full of great players," Scott said. "But I really believe we're on the right path now, and I'm optimistic."
Im Sung-jae and Joaquin Niemann, both of whom participated in the 2019 edition, also made the team, while Kim Joo-hyung, Corey Conners and Mito Pereira will make their debuts.
Immelman and Love will announce their captain's selections in early September to complete the 12-man teams.
