One man is thought to have collapsed inside the wall and when the second man and woman went inside to help him they too both collapsed.
The series of events began when a 69-year-old man went into the tank to undergo water maintenance. He collapsed shortly afterwards. The man's 68-year-old brother came into the tank afterwards and collapsed soon after.
The first man's wife, a 69-year-old women, entered the tank after the second man had collapsed.
All three died within a couple hours of each other.
When officers from the Hume Local Area Command arrived all three were already dead.
"From initial reports there were high levels of poisonous gas in the water tank," Superintendent Andrew Koutsoufis said at the scene.
The bodies had to be left in the tank overnight because of fumes in the tank. Police said they were "not sure" for how long.
"They all did a wonderful job in response to a really nasty incident," Supt Koutsoufis said.
The deaths are not being treated as suspicious.
Police said they were preparing a brief for the coroner.
Names of the family have not been released at this time.
"They need time to grieve," police said of the family.