Scott will return to Royal Melbourne Golf Club just three days after claiming the Australian Masters title at the same venue, while the world number two will represent Australia alongside Day, who has also had a top season in 2013.
While Scott has grabbed the headlines with his victory in the Masters in April and at The Barclays in August, Day has also had a solid year with top-three finishes at the WGC-Accenture Match Play Championship, Augusta (just two shots adrift of Scott) and the US Open.
The Australian duo should also be comfortable around Royal Melbourne with Scott able to pass on tips to Day following his triumph in the Australian Masters last week.
Scott had to endure a nervous finish on the final day as both Vijay Singh and Matt Kuchar pushed hard at different times throughout Sunday's play but the 33-year-old Australian eventually won by two strokes.
Kuchar should also take plenty of confidence into the World Cup after his second-placed finish last week, while the world number seven is also the reigning champion and is back to defend his title alongside Kevin Streelman.
The United States pair will also have history on their side as the USA have claimed the World Cup title 24 times - more than any other country.
South Africa are the second-most successful country in World Cup history with five victories and will be represented by Branden Grace and George Coetzee at Royal Melbourne, while Spain have won the title four times to sit equal-fourth alongside Australia on the all-time table.
Rafa Cabrera-Bello will represent Spain at a professional level for the first time in his career and cannot wait to step onto the course alongside team-mate Miguel Angel Jimenez, who was part of the Spanish pair who finished second in 2008.
Players will complete a 72-hole stroke-play event with the average scores of teams to decide the winner.
"It's the first time I will have represented my country in a professional team event, so I'm definitely looking forward to it," the 29-year-old said.
"I'm playing with Miguel, my good friend who I admire. He has played this event many times and has been successful in the past, so I'm excited to be playing with him.
"Spain have come very close to winning in recent years, so hopefully we can go one better this time.
"Even though it is mainly a stroke-play event, I'm sure we will be encouraging each other and looking out for each other's scores during the week."