The Amaranto showed Nicola the door following Sunday's 3-0 defeat at home to Parma, their fourth straight loss.
Their dismal run of form has seen Livorno drop to 19th place, three points adrift of safety at the halfway stage of the campaign.
A statement from Livorno read: "Livorno announces it has handed the reigns of the first team to Attilio Perotti."
Perotti, who was acting as technical director of Livorno prior to today's announcement, already guided the Amaranto in the 2011-12 campaign in Serie B.
The 67-year-old has not coached in Italy's top flight since guiding Empoli in the 2003-04 campaign.
Nicola had guided the Tuscan club to promotion to Italy's top flight last summer in his first season in charge.
He was sacked on Monday, with the club releasing a statement that read: "Livorno announces it has dismissed coach Davide Nicola.
"The club wishes to thank the coach for his professionalism and the work done."
Perotti's first game in charge will be on Saturday at Roma.