Serbia's Novak Djokovic arrives for a training session during the 2022 Wimbledon Championships on Sunday. AFP
In the absence of the banned Daniil Medvedev and injured Alexander Zverev, 20-time major winner Djokovic takes top seeding.
The 35-year-old defending champion starts his title bid against South Korea's Kwon Soon-woo, the world number 75.
Djokovic has extra motivation this year as Wimbledon will be his last Slam of 2022.
Novak Djokovic returns the ball during a training session in Wimbledon, southwest London, on Sunday. AFP
His continued refusal to get vaccinated means he will remain banned from entering the United States for the US Open later this summer.
Also adding fuel to the Djokovic fire is the chance to win a fourth successive Wimbledon title and join a select group.
In the Open era, only Bjorn Borg, Sampras and Roger Federer have managed to complete such a streak of dominance at the All England Club.
"As a seven, eight-year-old boy I've dreamt of winning Wimbledon and becoming number one," said Djokovic.
"Pete Sampras winning his first Wimbledon was the first tennis match I ever saw on the TV."
Murray, the Wimbledon champion in 2013 and 2016, is unseeded this year but remains a dangerous floater in the draw.
He made the Stuttgart grass-court final earlier this month before an abdominal injury forced him out of Queen's.
Wonder girl Coco Gauff continued her magical Wimbledon debut on Wednesday when she became the youngest player since 1991 to reach the third round.
Wimbledon is set to start in London on June 29, but the continuing spread of the virus has caused havoc with the sporting schedule and the grass-court Grand Slam could be the next major event to be delayed.
Roger Federer moved into the fourth round of a Grand Slam tournament for the 69th time on Saturday, overcoming a raucous home crowd and the last British man
"He was in my ear the entire match basically, especially when I was two-sets-to-love down. He was encouraging me. He was actually giving me tactics, as well. He was like, 'Hold your serve, get an easy first ball, then dictate, go to his backhand.' He was coaching me, literally," said Djokovic.
Her victory in the Women's singles badminton at the Commonwealth took her to completing a hat-trick of medals at the Games with a win over Michelle Li of Canada in the women's singles final in Birmingham.
She picked up her first victory since the 2021 French Open on Monday, beating Nuria Parrizas-Diaz 6-3, 6-4 at the women’s National Bank Open.
The six-time defending champions showed their opponents no mercy in sweltering conditions on the final day of sporting action in Birmingham.