Wales have not beaten one of the Southern Hemisphere's big three since they put the Wallabies to the sword in 2008 but Hook believes they are more than capable of repeating those heroics if they believe in themselves and perform for the full 80 minutes.
A win against one of more of the Tri Nations' giants would then give Wales a perfect spring-board into the Six Nations and their preparations for next year's World Cup.
"It starts here. We have to try to beat one of the big teams," said Hook.
"We beat Australia a few years ago but we have to beat one of them again. We obviously want to win all four games but we must at least win one or two of the big games.
"That will but us in good stead for the Six Nations and then pretty much straight into the World Cup. To have that confidence going into the World Cup, knowing that we have beaten one of the top teams, would be brilliant.
"It you look at the recent games, we're not far away. It is just sloppy penalties, mistakes and giving away soft tries which we know we can defend.
"We know we have the attackers in the team, we just need to believe in ourselves. It's just mental. It's only been in the last 20 minutes of games when we realise that we're still in it that we start to play, and then it's too late. So we have to start playing from the beginning.
"The boys are really excited, we have some massive games and we want to get that scalp. We have got belief in the squad but this is where the hard work begins."
Hook is particularly looking forward to making amends for Wales' disappointing showing against Australia last year where they went down to a 33-12 loss in Cardiff.
The Wallabies have since beaten South Africa twice and run the All Blacks close in the recent Tri Nations, playing a scintillating brand of attacking rugby along the way.
And having experienced how tough an opposition Robbie Deans' men can be last time out, Hook is expecting a massive challenge at the Millennium Stadium.
"They have some cracking players," added Hook.
"The way the game has gone they have the type of players that you want. They're great attacking players who are tactically aware. They're good with the ball in hand and in kicking terms as well.
"The game against Australia last year was one of the toughest games I've ever been involved in. They just threw around the ball. They were pretty good that day and we had no real answer to them."
Tickets are currently still available for all four of Wales' Invesco Perpetual Series matches against Australia (Sat 6 Nov 2.30pm), South Africa (Sat 13 Nov 2.30pm), Fiji (Friday 19 Nov 7.30pm), New Zealand (Sat 27 Nov 5.15pm).
Ticket-only packages are available in Thomas Cook and Going Places stores around Wales and the UK.
Tickets are also available online by clicking here, by phoning 08442 777888 or by calling into the WRU's cafe/store, The Cardiff Arms, 8 Westgate Street, Cardiff.