A member of the public was picking up bottles discarded on the side of the Olympic Highway and contacted the service.

Walla's Kylie Sim and another volunteer answered the call on Saturday afternoon.

"Obviously they weren't picking that can up," she said.

"I've heard of snakes getting their heads stuck in cans but I'd never actually seen it.

"We got there, and sure enough, she had jammed herself in there so well she was not getting out of this can.

"She was pretty lifeless - I wasn't sure if she was alive."

While Ms Sim held the snake, snippers were used to cut the snake free.

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She urged drivers not to throw rubbish from their cars.

"It would have been a pretty terrible way to die," she said.

"She was very thankful - once we got her free, she was on her way very quickly.

"They're tricky to catch and relocate at the best of times, let alone one that has been stuck without food."

Ms Sim has been a volunteer for six years.

"We've had a few in bizarre places at the moment; in laundry cupboards and under a school bag at a primary school," she said.