The mixed-teams event begins in Perth on Friday, with Australia pitted into what is effectively a group of death featuring tournament favourites the US and Great Britain.
The US charge will be led by world No.10 Taylor Fritz and No.5 Jessica Pegula, with the pair keen to defend their title from last summer.
Cameron Norrie will be part of the Great Britain team to take on Australia in the United Cup. (Lukas Coch/AAP PHOTOS)
Great Britain will wheel out world No.18 Cameron Norrie and No.56 Katie Boulter.
World No.12 Alex de Minaur and three-time grand slam quarter-finalist Ajla Tomljanovic headline Australia's team, with Matt Ebden and Storm Sanders set to combine for the mixed doubles.
There are six groups each comprising three nations, with each group winner advancing to the quarter-finals.
A quarter-final berth will also be handed to the best runner-up in both Perth and Sydney.
"It's a bloody tough group to be honest, probably the toughest there is," Hewitt said on Thursday.
"First of all we've got to worry about Great Britain. It will be two really tough singles matches.Â
"Hopefully we can go out and get the job done in the singles, but we'll be confident in the mixed if it comes down to that as well
"Team USA won it last year. They're very strong, especially their two main singles players.Â
"We've just got to give ourselves a chance. If we can go out there and do well tomorrow (against Great Britain), that gives us a chance to get through to the quarter-finals."
Australia are hoping to attract big crowds to their ties against Great Britain and the US at Perth's RAC Arena.
Hewitt, who was a fan favourite when the Hopman Cup was held in Perth, hopes his players feed off the energy.
"There's nothing better than playing in front of big, packed crowds," Hewitt said.
"I know from my experience playing here in Perth, the crowds come out in droves supporting our players.Â
"I think the guys and girls are really going to feed off that in our first two (ties), and you never know, hopefully that gives us a better chance to get into the quarters."
Doubles star Ebden is adamant Australia can buck the odds and contend for the crowd.
The Australian team TURNED UP to Rottnest Island to take the famous quokka selfie 🇦🇺🤳— United Cup (@UnitedCupTennis) Who did it best?@westaustralia @RottnestIsland @DestPERTH #westernaustralia #WAtheDreamState pic.twitter.com/iavX81pkyfDecember 27, 2023
Poland, featuring world No.1 Iga Swiatek and world No.11 Hubert Hurkacz, are tipped to be the main challengers to the US bid to go back-to-back, while Serbia will rely heavily on 24-time grand slam champion Novak Djokovic.
Germany have a strong team in world No.7 Alexander Zverev and three-time grand slam winner Angelique Kerber.Â
Greece, with world No.7 Stefanos Tsitsipas and No.9 Maria Sakkari, are also set to be strong contenders.
"I believe in our team," Ebden said. Â
"I think we've got world-class players. I think all six of us can play at any time.Â
"Whoever's required I would be confident in, but at the same time the event has brought basically every top 10 or top 20 player - men's and women's.
"So it's the best of the best. I think that's what we want to see.Â
"That's what we're here for - to test ourselves and use our Australian home advantage and, of course, we're going for the win."
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