The actress, who played Izzy Davies in the Channel 4 soap, will arrive in Weatherfield as Jenny - doctor Matt Carter's (Oliver Mellor) ex-girlfriend.
Jenny will clash with Matt's current girlfriend Tina McIntyre, played by Michelle Keegan, as she tries to win him back.
When Matt fails to stick up for Tina amid Jenny's insults during a double date, she pours a pint over his head and dumps him.
A show insider told The People: "We're going to see a good old fashioned catfight over the coming months.
"Michelle and Elize are real stunners but their characters are after the same man. So we're going to see some fireworks.
"Tina's already lost boyfriend Graeme Proctor this year. So it's going to be interesting to see how she copes with another, older woman moving in on her territory with Matt."
Since leaving Hollyoaks, Du Toit has gone on to appear in The Bill, Casualty and Waking the Dead.