Duley, who was 29 years old at the time of the murders, confessed to suffocating two of her three children, 2-year-old Devean C. Duley and 18-month-old Ja'van T. Duley, and then putting them in a nearby river to make it look like an accident.
She now faces from 60 years to life in prison if convicted for her crimes.
Winfrey interviewed Duley in 2010, not long after the murders, and plans to hold a follow-up with Duley, who has been held without bail for two years at the Orange-burg-Calhoun Detention Centre in South Carolina, where she awaits her sentence.
According to Entertainment Weekly, the interview will air in a new instalment of Oprah's Next Chapter.
The series, in which Winfrey conducts one-on-one interviews with public figures, is the most watched on the struggling OWN channel.
The OWN network launched earlier this year, and has experienced dismal ratings. To combat costs, Rosie O'Donnell's talkshow was cancelled after only five months on air.
Last week, 30 employees of the OWN network were laid-off and major changes to the channel are in the works.
The controversial interview with Duley may be another bid to increase viewership, like Winfrey's recent interview with Bobbi Kristina Brown shortly after her mother Whitney Houston's death.
Winfrey's Shaquan Duley interview is scheduled to air on April 1 on OWN.
Watch Oprah Winfrey interview Bobbi Kristina Brown below: