More than 50 of the region's healthcare workers at most risk of contracting coronavirus will be included in the first round of jabs this week.
They include workers at COVID-19 assessment clinics at Wollongong and Shellharbour hospitals and staff in Wollongong's busy emergency department.
With initial supplies of the vaccine limited, each worker has received an invitation from NSW Health and will this week board a bus to Liverpool Hospital's vaccination hub.
Wollongong ED head of department Dr Simon Binks said he wants to lead by example by getting the vaccine to protect himself, his colleagues and his community.
"This is the next step forward in terms of getting back to normal life," he said. "I'm confident the vaccine is safe, it's been used internationally in large numbers with minimal side effects.
"If it offers the same amount of protection demonstrated by research, then we will see less people with COVID, and those who do get the virus will have far less severe respiratory problems."
Registered nurses Jo Keough and Sharon Stewart remain on the frontline at Wollongong Hospital's COVID assessment clinic and are both "excited" to get the vaccine on Wednesday.
"This feels like the beginning of the end," Ms Keough said. "I feel really privileged to be an Australian and have complete trust in the Therapeutic Goods Administration, and its approval process.
"I'm relieved for my family, and all families in this country, as I believe this vaccine rollout will lead to less deaths and hospitalisations."
Ms Stewart added: "This will have a huge impact on our community members, socially, economically, emotionally and physically".
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The Illawarra Shoalhaven Local Health District staff will be among more than 35,000 critical staff in NSW who will be the first in Australia to receive the Pfizer vaccine.
"The first phase of the rollout is targeting those staff with the highest potential to come into contact with COVID-positive patients," ISLHD Executive Director Nursing and Midwifery, Deborah Cameron, said.
Around 1000 of these staff had been identified across the health district, Ms Cameron said, and as vaccine supply increased, more staff would be included.
"It has been so refreshing and rewarding to see such a positive response to the rollout," she said. "...The vaccine is not mandatory, but there's a great take-up from workers."
While staff would initially travel to Sydney, she said there were plans to establish a hub at Wollongong Hospital while outreach programs may also be set up so staff could get the vaccine closer to where they work and live.
Ms Cameron said Wollongong and Shellharbour staff were selected for the first week of the rollout due to community cases over the Christmas New Year period. In the coming weeks, workers from Shoalhaven Hospital would be called up too.
She said the past year had been difficult for frontline staff, and she believed the vaccine was a major step in getting back to normality.
"However we need to maintain our vigilance and attention to maintaining COVID testing rates - COVID hasn't gone away," she said.
The health district will provide more information in the coming weeks about further rollouts of both the Pfizer and AstraZeneca vaccines, including expanded access to the vaccine through regional vaccination sites.
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