The 24-time Grand Slam champion is 16 years Rune’s senior but doesn’t underestimate the challenge the Dane will pose when they close proceedings on Centre Court.
“Rune’s a spectacular player, no doubt. He loves the big stage, loves playing on grass. I think he’s a very, very tricky opponent,” said second seed Djokovic.
The 37-year-old is going for an eighth Wimbledon title and record 25th Grand Slam overall.
“It’s going to take my best tennis to win,” he added.
“I actually get along very well with [Rune]. He’s a very nice guy, always has been to me and to my team, and vice versa.”
The pair have met five times previously, with Serb Djokovic winning on three occasions, including the two most recent, on hard courts in 2023.
“I always try to be available to him for any practice or advice or guidance or anything like that,” said Djokovic.
“I think we have quite similar styles of tennis. But when it comes to playing on the court and competing, obviously we both have that fire. I’m sure that on Monday, we’ll see a lot of fireworks on the court.”
Following knee surgery just weeks before arriving at SW19, Djokovic is yet to win a match in straight sets at the All England Club but Rune said he still expects a “tough battle”.
“I’m expecting nothing but a great level from him. I know he did his surgery, but honestly I practised with him in the first week, and I saw him playing a little bit,” said the 15th seed.
“He seems like he’s playing very well, feeling confident.”
Elsewhere on day eight of the Championships, American 13th seed Taylor Fritz will take on German fifth seed Alexander Zverev on Centre Court while Australian ninth seed Alex de Minaur opens play on Court One against France’s Arthur Fils.
Kazakh fourth seed Elena Rybakina will open play on Centre Court against 17th seed Anna Kalinskaya with her sights fixed on the quarter-finals after a string of shock exits in the women’s draw.
After second seed Coco Gauff’s straight-set defeat by fellow American Emma Navarro on Sunday, 2022 Wimbledon champion Rybakina is the last of the top five seeds still in the competition.
Only two of the top 10 remain, with Italian seventh seed Jasmine Paolini through to the last eight.
Kazakhstan’s Yulia Putintseva sent number one seed Iga Swiatek out on Saturday and her reward is an outing on Court One against Latvian 13th seed Jelena Ostapenko in round four.
American 11th seed Danielle Collins takes on Czech 31st seed Barbora Krejcikova in the final match scheduled for Court One.
On court two, Ukraine’s Elina Svitolina, seeded 21st, will look to avoid slipping up against China’s Wang Xinyu
