Other big name men in action on Day 2 include Bernard Tomic, Jo-Wilfried Tsonga, Juan Martin Del Potro, Gael Monfils, Kei Nishikori, Fernando Verdasco, Milos Raonic, Gilles Simon, Marin Cilic, Radek Stepanek, John Isner and Grigor Dimitrov.
Among the big name women on top of Azarenka, Sharapova and Radwanska playing Round 1 matches include Svetlana Kuznetsova, Kaia Kanepi, Alize Cornet, Carla Suarez Navarro, Sloane Stephens, Jelena Jankovic, Simona Halep and Caroline Wozniacki.
On top of Hewitt and Tomic representing Australia on Tuesday, James Duckworth, Marinko Matosevic, Olivia Rogowska, Thanasi Kokkinakis, Nick Kyrgios and Storm Sanders will all be looking to win through to the second round as well.
The seeded players will also be looking to avoid upset defeats after the opening day saw the women's No. 6 (Petra Kvitova), 7 (Sara Errani), 12 (Roberta Vinci) and 23 (Elena Vesnina) losing as did the 12th-seeded man Tommy Haas.
The action on Tuesday morning begins at 11am EST on Rod Laver Arena with defending champion and world No. 2 Victoria Azarenka beginning her title defence up against Swedish world No. 90 Johanna Larsson.
Next up on Rod Laver Arena is Australian 21-year-old James Duckworth facing the huge task up against all-time great Roger Federer, who despite coming into the Australian Open as the No. 6 seed remains one of the tournament favourites.
It is then another Australian up next on Rod Laver Arena on Tuesday as the country's No. 1 Lleyton Hewitt begins his Australian Open campaign against Italian 24th-seed Andreas Seppi.
It is a tricky first round opponent for Hewitt but the 32-year-old deserves to enter the Australian Open full of confidence having already won the Brisbane International where he beat Federer in the final, and also down Andy Murray at Kooyong on Friday so far this summer.
The night session on Rod Laver Arena will then be headlined by world No. 1 Rafael Nadal taking on precocious Australian 21-year-old Bernard Tomic.
Tomic hasn’t done a lot over the past 12 months to endear himself to the Australian public either on or off the court, and on the court is lack of fighting qualities when he falls behind is something distinctly distasteful.
While it is a lot to expect him to beat Nadal on Tuesday, a competitive, fighting performance from the Australian could begin to turn his image as a spoiled brat around.
The night will then conclude on the main stadium with Russian glamour Maria Sharapova taking on a tricky American opponent in the colourful Bethanie Mattek-Sands who scored an upset win over Agnieszka Radwanska at the Sydney International.
Meanwhile, the action begins on Hisense Arena also at 11am firstly with former world No. 1 Caroline Wozniacki batting Spaniard Lourdes Dominguez Lino.
Next up is flamboyant Frenchman and former Australian Open finalist Jo-Wilfried Tsonga, entering the tournament as the No. 10 seed, taking on Italian Filippo Volandri.
World No. 5 Agnieszka Radwanska is up next on Hisense Arena taking on Kazakhstan's Yulia Putintseva.
The night session at Hisense Arena will then feature three-time finalist and reigning Wimbledon champion Andy Murray begin his 2014 campaign up against Japan's Go Soeda.
Action on Margaret Court Arena begins with Romania's 11th-seed Simona Halep taking on Poland's Katarzyna Piter.
Next up is Italian veteran Francesca Schiavone, in likely her last Australian Open, facing 20th-seeded Slovak Dominika Cibulkova.
Former world No. 1 Jelena Jankovic from Serbia then faces Japan's Misaki Doi before the day on Margaret Court Arena finishes with world No. 5 and Sydney International winner Juan Martin Del Potro facing American Rhyne Williams.
Then at night on Margaret Court Arena, 25th-seeded Frenchman Gael Monfils will face a tough task against the 99th-ranked American Ryan Harrison.
Australia's Marinko Matosevic faces a tough challenge up against 16th-seed Kei Nishikori with Nick Kyrgios taking on German Benjamin Becker and Thanasi Kokkinakis playing Dutchman Igor Sijsling,
And Australia's women in action will see Storm Sanders face Italian Camila Giorgi and Olivia Rogowska taking on Columbian Mariana Duque-Marino,
Other men's matches of note include Spain's Fernando Verdasco facing China's Ze Zhang, John Isner battling Martin Klizan, German Philipp Kohlschreiber playing Slovak Aljaz Bedene, Gilles Simon facing Daniel Brands, Milos Raonic playing Daniel Gimeno-Traver, Marin Cilic taking on Marcel Granollers, Radek Stepanek facing Blaz Kavcic, Robin Haase playing Donald Young and Grigor Dimitrov battling American Bradley Klahn.
While other women's action sees American young gun Sloane Stephens playing talented Kazak Yaroslava Shvedova, Carla Suarez Navarro playing Vania King, Alize Cornet battling Polona Hercog, Kaia Kanepi facing Garbine Muguruza, Svetlana Kuznetsova tackling Elina Svitolina and Sorana Cirstea facing New Zealand's Marina Erakovic.