Police said the four were fired upon in an "apparent trap" as they arrived on Monday morning.
The blaze broke out just before 06:00 local time (11:00 GMT) and officers had to evacuate nearby residents in an armoured car.
A gunman has been found dead at the scene, local police say.
The man was 62-year-old William Spengler, Webster Police Chief Gerald Pickering told media.
Spengler appeared to have shot himself in the head, Mr Pickering said.
He had previously served a 17-year jail sentence after being convicted of killing his grandmother.
Spengler's sister is unaccounted for and police fear she may have died in the fire, which engulfed seven houses.
The two dead firefighters were named by police as Tomasz Kaczowka and Mike Chiapperini.
Mr Pickering told reporters: "These people get up in the middle of the night to go put out fires; they don't expect to be shot and killed."
The two injured firefighters were named as Joseph Hofsetter and Theodore Scardino.
They are being treated for gunshot wounds at the Strong Memorial Hospital and are expected to recover.
Police spokesmen said the area was "an active crime scene" but that no more shooters were believed to be present.
'Senseless act'
Two of the firefighters had arrived in a fire engine and two in their own vehicles, police said. One wounded man managed to escape but the others were pinned down until the armoured car could be sent in.
Police evacuated residents and firefighters were then able to return to tackle the blaze.
Chief Pickering said: "Webster is a tremendous community. We are a safe community, and to have a tragedy befall us like this is just horrendous."
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