Rapidly-improving Belgium also made a winning start in the eight-nation event with a 2-1 win over Pakistan in another pool A match at the Kalinga stadium in the eastern city of Bhubaneswar.
Australia, the reigning world champions who are are seeking an incredible sixth successive title, struggled to keep pace with their rivals after England went into half-time 2-0 up.
Alastair Brogdon opened the scoring in the fifth minute with a spectacular back flick before the 23-year-old Ward increased the lead off a rebound from the post in the 27th.
Chris Ciriello pulled back one for Australia with a penalty corner but Ward, a last-minute replacement for the injured Harry Martin, made it 3-1 with a swift counter-attack three minutes from the end.
It was a disappointing start for the new-look Kookaburras, who were without retired veterans Liam de Young and Rob Hammond and the injured duo of five-time world player of the year Jamie Dwyer and Mark Knowles.
“It’s very disappointing to lose,” said skipper Eddie Ockenden. “We did not start well and that cost us in the end. We had our chances, but need to push up our game.
A delighted England captain Barry Middleton said the win was a good morale-booster for his team.
“It is a very good feeling to have secured the very first match in our favour,” said Middleton.
“Australia are a very tough team and this win today against them will definitely boost the boys.”
Thomas Briels scored Belgium’s match-winner in the 43rd minute after Muhammad Imran converted a penalty stroke for Pakistan in the 36th to equalise a 10th minute goal from Tanguy Cosyns.
World number four Belgium, who are playing in only their second Champions Trophy tournament, play Australia next on Sunday.
England take on Pakistan the same day.
In the opening pool B matches later on Saturday, the Netherlands meet Argentina and Olympic champions Germany clash with hosts India.
The teams have been divided into two pools for the preliminary league which will determine the line-up for the knock-out stage to be contested by all the eight sides.