A man will face court on Wednesday after a crash at Bolong, near Nowra.
Emergency services were called to Bolong Road just before 12.30pm on Thursday after a Toyota Camry and Holden Barina collided.
The driver of the Barina, a 79-year-old man, died at the scene.
His 72-year-old wife was airlifted to St George Hospital where she died on Saturday.
The driver of the Camry, a 35-year-old man, suffered serious injuries and was taken to Wollongong Hospital for treatment.
A two-year-old boy, who was a passenger in the Camry, remains in hospital in a serious condition.
On Monday, the 35-year-old was arrested at Wollongong Hospital and taken to Wollongong Police Station.
Officers from the Southern Region Crash Investigation Unit charged a 35-year-old man with two charges of dangerous driving occasioning death and dangerous driving occasioning grievous bodily harm.
He was refused bail and will appear at Wollongong Local Court on Wednesday.