The two deceased were travelling in the driver's carriage and were the male driver, 54, from the ACT and the female pilot, 49, from Castlemaine, Victoria.
V/Line - the regional public transport operator in Victoria - had reported some track faults in that section of line in the days leading up to the incident.
A dozen people were taken to hospital with non-life threatening injuries after yesterday's train derailment.
"The Sydney to Melbourne XPT train derailment near Wallan Station last night occurred over a section of track over which was awaiting maintenance", the union's state secretary Luba Grigorovitch said in a statement.
Transport authorities in New South Wales said there were approximately 160 passengers on board the train.
Wallan train accident Twitter
The service is now terminating at Albury for all south and northbound travellers.
Several other passengers were being treated for injuries, emergency services said.
Some passengers claimed they heard an onboard announcement saying the driver was trying to make up for lost time before the crash, but Insp Koger could not confirm this. Police said it may take days to clear the tracks.
In December, Infrastructure Australia knocked back a proposal to have an upgrade of the line from Melbourne to Albury placed on the nation's priority infrastructure list.
The business case noted that V/Line had a self-imposed speed limit of 15km/h on the 82-kilometre stretch between Broadmeadows and Seymour, which includes Wallan, due to "poor track quality" such as mud holes and tight rail alignments.
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