Etihad agreed last month to buy 49 percent of loss-making Alitalia in a 1.76 billion euro ($2.28 billion) rescue plan, giving it access to Europe's fourth-largest travel market and 25 million passengers.
Cassano, who has more than 35 years of experience in senior management roles, will take up the position immediately after the closing of the deal, Alitalia said in a statement.
The agreement will be closed after obtaining approval by regulators. A person familiar with the matter said on Tuesday EU regulatory clearance is expected by the end of the year.
Cassano has served as Chairman and CEO of Italian shipping company Grandi Navi Veloci, CEO of fashion company Benetton Group, and CEO of Fiat Auto Financial and Consumer Services.