The 33-year-old will begin his new leadership role alongside Kevin De Bruyne, Ruben Dias, Rodri and Bernardo Silva.
The Citizens were led to a historic Premier League, FA Cup and Champions League treble last season by midfielder Ilkay Gundogan, but he decided to end his seven-year stay at the club to join Barcelona this summer.
Gundogan is the latest legendary figure at Man City who has opted to seek pastures new after the likes of Pablo Zabaleta, Vincent Kompany, David Silva, Sergio Aguero and Fernandinho.
Following Gundogan's departure, Walker donned the captain's armband throughout pre-season despite speculation of a possible summer exit from the club, and has since started as captain in five of City's first six fixtures in all competitions.
The 33-year-old, who came "close" to joining Bayern Munich last month, committed his future to the Citizens by penning a two-year contract extension last week, and the experienced right-back has since expressed how honoured he is to have been recognised as one of the main leaders at the club.
Speaking at a press conference on Monday ahead of Tuesday's Champions League group-stage opener at home to Red Star Belgrade, Walker said: "The captain's vote has come and the five have been chosen and we will lead the team for the season and make sure everyone is in check and the fines are paid up.
"The order doesn't matter. It will be myself, Kevin De Bruyne, Rodri, Ruben [Dias] and Bernardo [Silva].
"(Wearing the armband) is something I've been very honoured to do and it's a privilege to lead this special group out. I will continue to do that.
"Hopefully, I will lead by example on and off the field to make sure we collect the trophies at the end of the season."
Walker has spent the last six years at the Etihad Stadium and has won 15 trophies under the tutelage of manager Pep Guardiola, making over 260 appearances across all competitions in the process.
De Bruyne, meanwhile, is the longest-serving player within Man City's current squad having spent the last eight years at the club, and the playmaker has established himself as one of the best players in world football during his legendary spell on the blue side of Manchester.
The 31-year-old has scored 96 goals and registered 153 assists for the Citizens in all tournaments, although he is yet to put his stamp on the new season as he is currently recovering from a long-term hamstring injury.
Like Walker, Bernardo Silva has spent the last six years at Man City and was strongly linked with a transfer away from the club earlier this summer, but the 29-year-old has instead signed a new three-year contract.
The versatile Portuguese playmaker scored his first goal of the new season and his 56th for Man City in last weekend's 3-1 win at West Ham United, while he has also provided 60 assists across his 311 appearances for the club.
Another integral cog in Guardiola's machine is midfield lynchpin Rodri, who is widely regarded as one of City's most important players and has developed into arguably the best defensive midfielder in world football, making 214 appearances and winning nine trophies since joining the club four years ago.
The 27-year-old Spain international scored the decisive goal to help Man City win 1-0 against Inter Milan in the Champions League final last season, and another standout performer in that historic triumph was centre-back Dias who has made a notable impression on the pitch and in the dressing room since arriving from Benfica in 2020.
While competition for places in defence is fierce at City considering the options at Guardiola's disposal, Dias, 26, is considered as one of the first names on the teamsheet and has played 138 times for the club in all competitions.
Dias, Rodri, Bernardo and Walker will all be in contention to start for Man City when they play host to Red Star in the Champions League on Tuesday, with the latter expected to continue wearing the armband.