The world number one opens play on Centre Court at 13:00 BST against Britain's James Ward.
Seven-time champion Roger Federer and French Open winner Garbine Muguruza also feature on day one.
Qualifier Marcus Willis, ranked 775, is one of eight Britons in action on Monday, with Andy Murray and Johanna Konta scheduled to start on Tuesday.
Monday's play begins on the outside courts at 11:30, with BBC coverage starting online at 10:00 and on BBC Two and 5 live sports extra at 11:30.
Djokovic arrives at the All England Club as the new French Open champion, holder of all four Grand Slam titles and on course for the first calendar-year Slam since Rod Laver in 1969.
The 29-year-old is a strong favourite to become only the fourth man in the Open era to win a hat-trick of Wimbledon titles.
"The situation this year is quite different because I'm coming in with a Roland Garros title for the first time," said Djokovic. "That gives me a lot of confidence."
Asked about facing a British player in his opening match, Djokovic said: "It's going to be the first match on the untouched grass.
"That's probably one of the most special matches that you get to experience."
Federer, 34, is the number three seed and is expected to face Djokovic in the semi-finals, although the Swiss lacks his usual number of matches after struggling with injuries all year.
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Second seed Murray appears the most likely to threaten Djokovic, having finished runner-up to the Serb at the year's first two Grand Slams in Australia and France.
Defending champion Serena Williams remains the woman to beat as she chases a seventh Wimbledon and 22nd major title, which would draw her level with Steffi Graf in the all-time list.
However, the 34-year-old American has not won a Grand Slam since last year's Wimbledon, with Muguruza beating her in France and rising to two in the world rankings.
Britain has 15 players in the singles draws this year, with seven there by right through their rankings, seven given wildcards and one coming through qualifying.
That is Willis, the 25-year-old who had not played a tournament since January and had to win six matches in pre-qualifying and qualifying to reach the main draw.
According to the ATP World Tour website, Willis' 2016 earnings amount to $64 - his performances so far in Wimbledon qualifying have seen him pocket £30,000.
Another victory over Lithuania's world number 53 Ricardas Berankis could set up a dream second-round match against Federer, as well as taking his pay packet to £50,000, more than half of his career earnings to date.
"I've always believed in myself, believed I could play really good tennis, but I can't really expect to qualify for Wimbledon," said Willis.
"I just took it one match at a time and now in the main draw I'll do the same there."
Six British men are in action on Monday, with Kyle Edmund playing France's Adrian Mannarino, Brydan Klein up against Frenchman Nicolas Mahut, Alex Ward facing Belgian David Goffin, and Dan Evans taking on German Jan-Lennard Struff.
In the women's draw, former junior champion Laura Robson plays fourth seed Angelique Kerber and Naomi Broady faces Ukraine's Elena Vesnina.
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There have been only eight championships - the last of them six years ago - without rain interruptions since 1922, and 2016 looks unlikely to add to the list.
The 130th championships will host up to 39,000 spectators on each of the 13 days, with more than 700 players in qualifying and the main draw competing for a record prize fund of £28.1m.
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Both singles champions will take home £2m, while just making the first round guarantees a player £30,000.
Spectators will consume about 28,000kg of strawberries, 7,000 litres of cream and 29,000 bottles of champagne, some of it almost certainly under the Centre Court roof.
The weather forecast suggests rain will feature during the first week of the tournament, but the roof at least guarantees tennis throughout.
"Not a complete washout, but through the first few days I'm expecting some rain," said BBC Weather's John Hammond.
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The BBC will have comprehensive coverage of Wimbledon across TV, radio, online and social media, with 153 hours scheduled across BBC One and BBC Two.
Former world number ones Lleyton Hewitt and Jim Courier, and former British number one Annabel Croft, have joined the BBC TV team, led by Sue Barker, while Radio 5 live will broadcast more than 100 hours of action.
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Top seed Novak Djokovic will begin the defence of his Wimbledon title when the tournament gets under way on Monday.