Manager Antonio Conte will take a week off before flying to London to finally take charge of Chelsea.
The 46-year-old was close to tears as he gave his last press conference as head coach of the Italian national side.
Italy impressed during Euro 2016 but crashed out after a heartbreaking penalty shootout against Germany on Saturday night.
"The decision to leave the national team after two years was taken early and I don't deny there were moments when I'd have liked to have the opportunity to continue," Conte told reporters after Italy's defeat against Germany.
"But, because of certain developments, I wasn't able to go back on that.
"In November I thought I was continuing with the national side. Then I told the president of the Italian football federation of the great opportunity to join Chelsea Football Club.
"I wanted to return to the cut and thrust of club football. Now, I have the opportunity to start this exciting adventure.
"Now I'll take seven days off to charge my batteries and shift a bit of this disappointment before taking over at Chelsea. I know it will be a difficult challenge but it's one I will cherish."