Napoli have been charged over alleged match-fixing in an Italian league game against Sampdoria on the final day of the 2009-10 season.
The club, their former third choice goalkeeper Matteo Gianello and ex-footballer Silvio Giusti will go before the federation's disciplinary committee after information was passed from a criminal investigation in Naples.
Samp won the game and entered the preliminary stage of the Champions League.
Current Napoli defenders Paolo Cannavaro and Gianluca Grava have also been charged for failing to report the alleged fix.
The development is part of a wide-ranging criminal and sporting probe into illegal betting and match-fixing in Italy which have already led to several arrests and bans.
Meanwhile, Napoli have also been fined €150,000 by UEFA for poor stadium organisation, ignoring security directives and the inappropriate behaviour of their supporters during a Europa League match.
The European governing body has also threatened the Serie A club with playing a European match behind closed doors if the issues at their Stadio San Paolo resurface within the next five years.
A UEFA statement said: "Italian club SSC Napoli have been punished by the UEFA Control and Disciplinary Body for the inappropriate conduct of their supporters, insufficient organisation in the stadium and non-respect of UEFA directives related to stadium security at their UEFA Europa League Group F match against Swedish opponents AIK on 20 September."
Napoli will also be banned from selling tickets for parts of the main stand for their next European game at home to Dnipro on 8 November unless they can provide "a report from an independent construction company which confirms, with photographic evidence, that the necessary repair work has been carried out and that the aforementioned stands meet all the relevant spectator safety standards".
UEFA said if satisfactory repairs have not been carried out by 6 November they could prevent European matches taking place at the stadium.
Napoli have three days to appeal the decision.