The Serie A strugglers had only installed Attilio Perotti in the position last week following the departure of Davide Nicola, but he proved an unpopular figure with the club's fans and guided his charges to a 3-0 defeat at Roma last time out.
Perotti subsequently stepped aside, with former boss Nicola widely reported to be in line for a comeback.
However, president Aldo Spinelli has overlooked Nicola in favour of recruiting ex-Parma, Chievo and Sampdoria coach Di Carlo, who spent one season at Livorno as a player in 2000-01.
Currently 19th in Serie A, Livorno will officially unveil their new coach at a press conference later on Tuesday.
Di Carlo's first match in charge will be a home clash against fellow strugglers Sassuolo on Sunday.
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