The Azzurri have been without a permanent head coach since Gennaro Gattuso resigned in April following Italy’s failure to qualify for a third consecutive World Cup.
Italian Football Federation (FIGC) president Giovanni Malago revealed earlier this week that talks had taken place with Guardiola, who left Manchester City this summer after a decade in charge.
He also suggested the federation could make salary “exceptions” to secure the Spaniard.
However, FIGC technical director Paolo Maldini confirmed on Thursday that Italy’s first approach was made to former Azzurri midfielder Ancelotti, who is currently managing Brazil.
"We cannot hide the fact that we also spoke to Carlo before talking to Pep," said Maldini during a news conference per BBC.
"Frankly, it seemed right to start with those we considered the best in the world."
Guardiola enjoyed a hugely successful decade in England, guiding Manchester City to six Premier League titles, three FA Cups, five League Cups and the UEFA Champions League.
Former Italy managers Antonio Conte and Roberto Mancini, along with Andrea Pirlo, have also been mentioned as potential candidates for the vacant position.