Jamaica's Bolt, an eight-time Olympic gold medallist, will be the star attraction at the first Nitro Athletics event in Melbourne on Saturday.
It includes both traditional and new events, such as the elimination mile.
"This will be track and field as it's never been seen before," said Bolt.
The 30-year-old learned last week he would have to hand back one of his nine Olympic gold medals after Jamaican team-mate Nesta Carter tested positive for a banned substance.
Bolt said at the time: "I'm not happy, but it's just one of those things that happen in life."
He is now preparing to captain the All-Stars in an event he says will bring "something different" to world athletics.
Lord Coe, head of athletics' governing body, said: "Athletics, in its traditional form, remains the cornerstone of the Olympic Games.
"However, we need innovation and more opportunities for our athletes to interact with fans and show their personalities."
Athletics Australia president Mark Arbib says it is "the sports entertainment product track and field needs to move athletics beyond the existing format of one-day athletics meets".
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He believes it will be a "game-changer", an event showcasing a mix of power, endurance, technique and teamwork disciplines across sprints, distance, field and Para-athletics events.
Cue mixed events, medley relays and target javelin, with countdown clocks, athletes wearing microphones and fluorescent blocks and batons.
Points are awarded for each of the 12 events, as the six teams compete over three one-day meetings at Melbourne's Lakeside Stadium.
Four-time Olympic 400m medallist Christine Ohuruogu will lead the England team against Bolt's All-Stars, Australia, New Zealand, China and Japan.
"I really do think Nitro is going to be a huge success and I think everybody around the world is watching to see how it goes," said the 32-year-old two-time world champion.
Middle-distance runner Michael Rimmer and sprinter Bianca Williams are among those competing alongside Ohuruogu, while Bolt's team will include his Jamaican relay team-mates Asafa Powell and Michael Frater.
"It is going to be great, going to be something different. Like cricket and Twenty20," added Bolt, who confirmed he has no plans to extend his career beyond this year's World Championships in London
"I feel it will catch on. It's going to bring a lot of excitement to the sport."

The 19-year-old defensive midfielder has joined the Premiership leaders on a four-year deal after a £2.8m fee was agreed with Russian club Krasnodar.
"All I'm interested in at the moment is really progressing," Kouassi said.
"I really feel this is the best place for me at the moment to progress, to become better."
Captain Scott Brown played his 400th game for Celtic in Wednesday's 1-0 league win over St Johnstone and Nir Bitton, Callum McGregor and Liam Henderson have also played in central midfield areas this season, with Stuart Armstrong and Tom Rogic tending to play further forward.
"I'm not getting worried about it," Ivorian Kouassi said through an interpreter.
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"At the moment, since I haven't played for a wee while, I need to get back to full fitness then after that the coach is going to decide.
"When you play alongside players with such experience, you learn a lot. I expect players such as Scott Brown to really help me and maybe guide me.
"There's lots of great players that have come to Celtic before. It's got a great, great coach at the moment."
Uncapped at senior level, Kouassi played in the Europa League with Krasnodar and has watched Celtic playing in the Champions League, including this season's matches in Group C, which also contained Barcelona, Borussia Monchengladbach and Manchester City.
"It's something that I'm really, really happy about because it's the top," Kouassi said on the prospect of playing in next season's tournament. "It's the best you can get in European football.
"This is going to have an impact. Celtic is not a small club so hopefully, this will have an impact on my international career with Ivory Coast."
England will provide one of five teams competing against Usain Bolt's All-Stars in a new athletics event IAAF president Lord Coe says will "revolutionise" the sport.
[NEXT_CONCEPT]
New Celtic midfielder Eboue Kouassi is "not getting worried" about the competition he faces for a place in Brendan Rodgers' team.