Alcaraz, who stunned seven-time champion Novak Djokovic in a five-set final in 2023, is looking to become just the sixth man to complete the French Open-Wimbledon double in the same season.
Also in action on the opening day are world number one Jannik Sinner, US Open champion Coco Gauff and Australian Open winner Aryna Sabalenka.
AFP Sport looks at three matches to watch on Monday:
Carlos Alcaraz v Mark Lajal
-- Defending champion Alcaraz, still only 21, is chasing his fourth Grand Slam title and hopes to become only the sixth man after Rod Laver, Bjorn Borg, Roger Federer, Rafael Nadal and Novak Djokovic to win the French Open and Wimbledon back-to-back.
"I want to put my name on that short list to win Roland Garros and Wimbledon in the same year. I know that there's going to be a really difficult and big challenge for me, but I think I'm ready to do it," said the third-seeded Spaniard.
On Monday, he faces Estonia's qualifier Mark Lajal, a 21-year-old who had never won a Grand Slam qualifying match let alone a main draw tie before last week.
Lajal, the son of a motocross rider, has just two wins on the main tour in his career but if his playing statistics don't stand out, then his dreadlocked, blond hair style certainly turns heads.
"I've had them for a very long time. It has kind of become a big part of me and my image. A lot of people know me just from my dreads. I enjoy it and I think it's cool," he said.
This time last year, Lajal was losing a first round match at a second-tier Challenger event in the US and earning a paltry $780.
For making the first round at Wimbledon he is guaranteed $75,000.
Jannik Sinner v Yannick Hanfmann
The 22-year-old Sinner is alongside Alcaraz in the vanguard of tennis's next generation.
He won a maiden Slam at the Australian Open and then deposed Novak Djokovic as world number one, becoming the first Italian man to reach such heights.
Sinner made the quarter-finals at Wimbledon in 2022 and semi-finals last year where he was swept away in straight sets by Djokovic.
He arrives in London having captured a maiden grass-court title in Halle.
On Monday, he faces Yannick Hanfmann, the German world 95 who suffers from a hearing impairment in both ears.
Hanfmann has been defeated in the first round in both of his main draw appearances at Wimbledon.
Sinner got the better of him in their only meeting at the US Open in 2023 where the German won just five games in their first round clash.
Brenda Fruhvirtova v Mirra Andreeva
In a battle of two 17-year-olds, Russia's Andreeva finds herself in the unusual position of the senior player, born four weeks before her Czech opponent in April 2007.
Andreeva, seeded 24, made the semi-finals of the French Open earlier this month, stunning second seeded Australian Open champion Aryna Sabalenka in the last-eight.
Fruhvirtova arrives at Wimbledon on a career-high 88 and is making her main draw debut.
Monday's match will be the first time since Agnieszka Radwanska and Victoria Azarenka clashed in 2006 that two women yet to turn 18 have met at Wimbledon.
