From Sunday August 17, Whale will stand in for LBC's regular late night host Clive Bull, who is on holiday, presenting six live phone-in shows from 10pm to 1am each night.
The appointment marks a return to LBC for Whale, who hosted a weekend afternoon show on the station in 1994.
Whale said: "I'm really excited to be going back to LBC 97.3, where I've worked before.
"LBC was always very important to me, especially programmes hosted by the late Adian Love, as he was one of my inspirations. And I'm also very excited to prove that James Whale and Ken Livingstone can work together."
LBC has also announced that former London mayor Livingstone will be hosting his own weekend talk-radio show, stating on Saturday August 30 and airing live between 10am and 2pm every week. His permanent appointment follows his debut on LBC earlier this year, when he hosted the weekday afternoon slot during regular presenter Jeni Barnett's holiday.
In May, controversial presenter Whale joined Play Radio UK to broadcast a series of shows live on the internet. That same month he also joined shopping channel Bid TV in an evening slot.
Whale was sacked from TalkSport, where he had spent 13 years, when he broke Ofcom's political impartiality rules by urging listeners to vote for Boris Johnson in the London mayoral elections.
Jonathan Richards, LBC's programmes director, said: "[Whale] is a class act who appreciates the art of great conversation and revels in a commercial radio environment.
"I'm also delighted that Ken Livingstone is joining our team of intelligent and creative presenters on a permanent basis. Ken brings unique insight to LBC 97.3 after eight years as mayor."
Whale began his career as a talk radio host in 1974 at Metro Radio in Newcastle. In the 1990s, he fronted the eponymous James Whale Show on ITV.