The 34-year-old - who is most noted for her roles as Mandy Salter in EastEnders and Bad Girls inmate Janine Nebeski - is to play Cindy Cunningham's (Stephanie Waring) estranged best friend Savannah and will appear in all five hour-long episodes.
Savannah's intentions for making contact with her old pal after so many years, however, may not be as genuine as Cindy originally believes.
More recently, Stapleton made a short-lived appearance in Emmerdale as Eli Dingle's (Joseph Gilgun) wayward friend Danielle Hutch.
Heading up the second run of Later is Hollyoaks' former leading producer Bryan Kirkwood.
Speaking of the new series, he said: "I'm so excited to be back at Lime Pictures and working on the next instalment of Later. Last year was a real departure in which we saw the Hollyoaks late-night series grow up and this year is set to continue in the same vein."
He added: "We've selected some of the best-loved Hollyoaks characters, put them in romantic, funny and dangerous situations and I'm hoping viewers love the result."
Production of the five 60-minute instalments is well under way in preparation for transmission during the final week of September.
Other featured storylines include an unlikely wedding, the teens attending a music festival, a trip to London for the McQueen clan and a dramatic boot camp plot with Sarah (Loui Batley), Zoe (Zoë Lister) and Lydia (Lydia Kelly) which ends in tragedy.
> Click here to read more about this year's episodes in Soap Scoop