The Casey Anthony story will start the second season of "How It Really Happened With Hill Harper" on HLN.
Harper, an actor on ABC's "The Good Doctor," looks at high-profile cases on the series.
The Anthony story will air as a two-hour episode, with limited commercial interruptions, at 9 p.m. Sunday, the show's regular time slot.
Anthony was acquitted of murder in 2011 in the death of her daughter, Caylee.
A preview with promotion from HLN: "Why was Anthony lying? And where was Caylee? This extraordinary two-part episode follows the twists and turns of this bizarre case and unbelievable trial."
The series will draw on CNN and HLN anchors and correspondents to provide expert analysis on stories they covered. The series debuted in January and looked at the Menendez brothers murder trial, the fatal plane crash of John F. Kennedy Jr. and the death of Anna Nicole Smith.
In the second season, the other episodes are:
"The Gianni Versace Murder" on Oct. 22.
"The Mystery of Heaven's Gate" on Oct. 29.
"Who Killed Chandra Levy?" on Nov. 5.
"The Strange Case of the Killer Nanny" on Nov. 12 focuses on Louise Woodward.
"George Michael's Final Days" on Nov. 19.
The series will be preempted Nov. 26 for Thanksgiving holiday weekend.
"The Monica Lewinsky Scandal, Parts I and II" will be two hours on Dec. 3.
"Did Scott Peterson Murder Laci? Parts I and II" will be two hours on Dec. 10.