Since 1992 Australia have won a medal at every Olympic tournament and the World Cup winners will be the favourites to clinch what would be only their second gold medal.
The Kookaburras, who recently beat India in a penalty shootout in the Champions Trophy final, only managed a bronze four years ago in London despite being overwhelming favourites.
Their London heartbreak triggered a lot of soul searching from the men in gold and green.
"Yeah, we had to do a lot of long hard looking at ourselves, but it paid off ultimately," 32-year-old Glenn Turner, a member of the Australia squad, said.
"Leading up to London we had trained really hard but there was a very different feel to the squad compared to this time around.
"After London we got a psychologist in and we started to get to know each other a lot better."
Mark Knowles and Jamie Dwyer, a five-time International Hockey Federation player of the year, provide Australia with a wealth of experience since Rio will be their fourth Games.
Knowles said the team, who face New Zealand in their first match, would settle for nothing but gold in Brazil.
"When we go to the Olympic Games as the Australian men's hockey team we want to win, we don't want to get bronze, just make the semis or play off for fifth," he said.
Also in Australia's group are Great Britain, Belgium, Spain and the host nation.
Germany, who triumphed in Beijing and London, are ranked third in the world. The squad chosen by head coach Valentin Altenburg contains five Olympic gold medallists from London.
The champions have been pooled with the Netherlands, Argentina, India, Ireland and Canada, with the top four teams from each group advancing to the quarter-finals.
Once-mighty India are the most decorated nation in the sport's Olympic history but the South Asians won the last of their eight gold medals way back at the Moscow Games in 1980.
Their strong build-up, claiming silver at the Champions Trophy, has again boosted optimism among fans in the nation of 1.25 billion people.
On the women's side, the Netherlands have captured seven world titles and been to every Olympic Games since 1984, winning three gold, one silver and three bronze medals.
The world's top-ranked side will be the heavy favourites to add to their gold medal tally in Rio.
(Editing by Ken Ferris)
