Former goalkeeper Matteo Gianello, now a free agent, has been accused of attempting to fix the outcome of Napoli's Serie A match at Sampdoria in 2010, with defenders Gianluca Grava and Paolo Cannavaro standing accused of failing to report the incident having been approached.
A statement on the federation's official website figc.it read: "The FIGC can confirm that, following an investigation by the public prosecutor of Naples, the federal prosecutor will open disciplinary proceedings in relation to the Sampdoria-Napoli match of May 16, 2010.
"Matteo Gianello, Napoli's former player, and Silvio Giusti, Napoli's former coach, are accused of violating Article 7 (sections 1, 2 and 5) of the sporting code of justice.
"Between them, they are accused of attempting to alter the outcome of the match to secure a victory for Sampdoria in exchange for money.
"(They are) also accused of having approached colleagues Paolo Cannavaro and Gianluca Grava, from whom they received a refusal.
"But Cannavaro and Grava stand accused of violating Article 7 (section 7), in failing to disclose the approach to the federal prosecutor."
Napoli have also been deferred as the club involved at the time, and could face a points deduction.
Juventus head coach Antonio Conte was handed a 10-month suspension in August, subsequently reduced to four months on appeal, for his failure to report match-fixing while in charge of Siena.
Conte's former club subsequently accepted a six-point deduction for their role in the 'Calcioscommesse' scandal, with a host of sides from both Serie A, B and the Lega Pro receiving demotions, points penalties and fines across a turbulent summer in Italy.
Former Bari defender Andrea Masiello was given a 22-month suspended prison sentence after admitting scoring an own goal during a relegation decider, with ex-Siena defender Emmanuele Pesoli chaining himself to the headquarters of the FIGC for four days in protest against a three-year ban.