Paramedics treated Ms Lewanski at the scene before they took her to St George Hospital, where she later died from her injuries.
She had just begun a librarian internship at the University of Technology in Sydney, her father, Henry Lewanski, told the Daily Mail Australia.
"She is a beautiful girl, words can't describe how we are feeling right now," he said.
"People should be able to be safe in the street."
The young woman has a twin sister and older brother, Steven, who paid tribute to his lost sibling on social media.
"Nicoles (sic) beautiful soul has shed this worldly vessel," he wrote on Facebook.
Mr Nealon, 35, refused to undergo a roadside breath test at the scene of the crash, but was arrested and taken to Royal Prince Alfred Hospital for mandatory blood and urine testing.
Police allege, the tests returned a positive blood alcohol reading of 0.199 - almost four times the legal limit.
He has been charged with six offences including aggravated dangerous driving occasioning death, drive recklessly, furiously, or at a speed or manner dangerous and drive with high range PCA (prescribed concentration of alcohol).
His licence was suspended and he was refused bail. He will appear in Sutherland Local Court later today.
Footage from the scene showed a blue ute with significant damage to its front end. Its bonnet was torn off, with debris scattered along the road.
All northbound lanes of the Princes Highway were closed at the crash site as police and emergency services responded. Traffic crews diverted cars around the scene, The Sydney Morning Herald reports.
Anyone who saw the crash, who has not yet spoken to police, has been urged to contact Crime Stoppers on 1800 333 000.
A report will be prepared for the Coroner.