Xhaka will take the armband from another former Arsenal player, Stephan Lichtsteiner, who retired from football last month.
Xhaka, who has occasionally led his country in the past, will begin his substantive role in Thursday’s UEFA Nations League game against Ukraine.
The 27-year-old made his debut for the Switzerland national team in 2011 and has so far made 82 appearances for the Red Crosses, scoring 12 goals.
Xhaka has represented Switzerland at the 2014 and 2018 FIFA World Cups as well as the 2016 European Championships.
"It's a real pleasure to meet again with the national team after a ten-month break," Xhaka said.
"As the new captain, I am extremely proud to be able to play for my country, and moreover to represent it in the captain's role. It's a dream come true.
"We are happy to be able to count on your support and we promise we will do everything to bring you joy in the upcoming campaign and also in the future."
Xhaka will hope his new role will be more fruitful than his last at Arsenal.
The former Borussia Monchengladbach man was named Arsenal captain in September last year but lasted just over a month in the role before he was stripped off the captaincy and replaced by Pierre-Emerick Aubameyang after he was involved in an angry confrontation with the club’s fans in a Premier League game against Crystal Palace.
