They are the most successful nation in women's Olympic Hockey, with three gold medals - in 1988, 1996 and 2000 - and are making a record eighth appearance.
In the late 1990s and early 2000s, the all-conquering Hockeyroos, under the guidance of Ric Charlesworth, who has since restored the men to world number ones, were the team to beat.
However, they have not won a medal in the last two Olympics Games, but Commens believes that could be about to change.
'I believe this is the playing group that can bring a new golden era to Australian women's hockey, and that begins here at the Olympic Games,' said the coach, whose side have the honour of starting the tournament against neighbours New Zealand.
'The players are steadily improving and our first game is vital for our chances, but it will be a tough game against a really quality opponent.'
New Zealand coach Mark Hager, a former Australia captain, believes set-pieces could be key.
'They've got a couple of good (penalty) corner specialists who've really improved over time, and if you look at the corner attack from both teams, we've both been pretty successful against each other,' he said.
'Whoever defends them or executes them could possibly win the game. We know that they are going to come out at us, they are a team that likes to pressure.'
Defending Olympic champions Netherlands, who are aiming to become the first nation since Australia in 2000 to win back-to-back golds, have failed to win a medal only once in seven Games since the women's sport was entered in 1980.
Beijing 2008 silver medallists China play Republic of Korea, while world champions Argentina take on South Africa.
Hosts Great Britain play Japan, the last team to qualify for London 2012 back in May, while Germany face the USA.