Woman, baby boy missing after Sydney fire (AAP)

AAP A man has been rescued after a fire ripped through a convenience store in Sydney's inner west.

Firefighters say a woman and her baby son are missing after a fire tore through a Sydney store.

Emergency services are involved in a delicate rescue operation with three people unaccounted for after a blaze destroyed a convenience store and adjacent units in Sydney's inner-west early on Thursday.

A search is on for the 31-year-old woman, her 12-month-old son and an unrelated 30-year-old man with firefighters concerned about the stability of surrounding buildings on Darling Street in Rozelle.

Emergency services are attempting to shore up the walls of the surrounding buildings and put cameras into voids.

Dogs are being used to try to locate the missing trio who lived in neighbouring apartments.

"It's still a rescue and horrific as the scene is down there we are still holding out hope that there are some survivors," NSW Fire and Rescue (NSWFR) Superintendent Paul Johnstone said.

"We always hold out hope. It's not a recovery operation and we're still hoping to find some survivors."

State Emergency Service (SES) volunteers with sniffer dogs have arrived at the scene to help scour the rubble of the burnt out building.

It is understood the missing mother and child lived in a unit above the convenience store.

The woman's husband was not home when the explosion shook the street.

The other missing man, a 30-year-old, lived in a neighbouring unit.

Police Superintendent Clive Ainley said there was a report of a car driving away from the scene when the explosion occurred.

"I don't know what part that car plays in the investigation at this time," he said.

Darling St is expected to remain closed off for the rest of Thursday and possibly into Friday morning.

Supt Johnstone said an initial blast about 4am on Thursday had blown out windows up to 100m away.

Neighbour Anthony Carroll, who lost everything in the fire, said he was asleep in a unit next door where he lived with his father when he heard a massive explosion.

"Within 30 seconds my room was full of smoke," he said.

"I just grabbed what I've got on and got out of there.

"There were people screaming and yelling and people trapped in the place next door so it was pandemonium.

"No one knew what was going on. I've been a bit emotional about it."

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