Marin Cilic of Croatia will face Fabio Fognini of Italy in the opening rubber of their Davis Cup first-round tie on Friday.
Andreas Seppi, who has risen to a career-high ranking of 18, and Ivan Dodig will follow them.
Saturday's doubles pits Simone Bolelli and Paolo Lorenzi against Mate Pavic and Nikola Mektic.
The reverse singles on Sunday sees Seppi face 14th-ranked Cilic in a rematch of their five-set Australian Open third-round tie which was won by the Italian.
Italy is looking to win its first World Group tie since 1998, when it finished runner-up. Croatia won the Davis Cup in 2005.
The winner faces either Spain or Canada in the quarterfinals.