The more than 500 portraits will be linked to online records already available through the National Archives of Australia.
The crisp black and white images show young men in uniform, hair done and beards shaven, ready for battle.
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Veterans Affairs Minister Warren Snowdon told his own story of using the archives to discover information about relatives who volunteered for war.
"I had grand uncles at Gallipoli ... I wasn't aware of it until this year," he told reporters at the archives in Canberra on Friday.
The archives were important for anyone who wanted to make a connection with a family member who died in battle and was buried in a foreign land.
"I think it's very emotional," Mr Snowdon said.
The photos were discovered by archives staff member Courtney Page-Allen at London's Imperial War Museum and form part of a collection of 16,000 WWI images.
One of the records pieced together tells the story of Lieutenant William Allen.
He joined the army in August 1914 and fought with 4th Light Horse Regiment at Gallipoli before being killed in action in February 1917 at Holly Ridge in France.
Included in the collection is a letter from Allen's mother written to the Army Records Office in the wake of her son's death.
"I was his widowed mother and he was my only child," Mrs Allen writes.
"My late husband his father died when he was an infant, three weeks old."
It is just one tragic story from a war filled with them.
Some of the portraits and accompanying stories are available at www.dva.gov.au and further information can be found at www.mappingouranzacs.naa.gov.au
