Madrid's 4-1 extra-time win over city rivals Atletico Madrid in Lisbon in May ended their 12-year wait for a 10th European Cup and they now look even stronger after a characteristically extravagant close-season recruitment drive.
Rodriguez, Toni Kroos and Keylor Navas arrived at the Bernabeu after impressing at the World Cup and all are in line to feature at the Cardiff City Stadium.
The first glimpse of 80-million-euro ($108 million) playmaker Rodriguez in a Madrid shirt is keenly anticipated after he dazzled for Colombia in Brazil, scoring six goals to win the Golden Boot.
With the 23-year-old former Monaco playmaker joining Cristiano Ronaldo and Gareth Bale in the Spanish capital, Madrid now possess three of the four most expensive players of all-time.
The trio could grace a pitch together for the first time in Cardiff, but like Kroos, who arrived from Bayern Munich after starring in Germany's World Cup triumph, Rodriguez is short of fitness and unlikely to start.
Along with Costa Rican goalkeeper Navas, the pair only returned to training last week and coach Carlo Ancelotti has admitted that his players are some way short of peak condition.
"We had to give holidays to some players until August 5," said the Italian.
"Therefore, we haven't had much time to prepare for the game. We need to try our hardest in August to prepare the players in the best way possible for the new season."
The Super Cup is one of six trophies that Madrid could win this season, but they are still searching for their first pre-season victory after two defeats and a draw on their tour of the United States.
One player who seems certain to start is Welsh forward Bale, who was born and raised in Cardiff and went to school just four miles (6.4 kilometres) from Tuesday's match venue.
Scorer of the decisive second goal in the Champions League final, the 25-year-old found the net twice in the US and is relishing the prospect of playing in front of his home crowd.
"I knew the Super Cup would be played in Cardiff a good 18 months ago," Bale told Spanish newspaper Marca.
"When I came to Real Madrid it was always a dream of mine that if we could win the Champions League, we could play in Cardiff. Now that dream has come true."
Tomorrow's opponents will carry special significance for Bale, for it was against Sevilla last October that he scored a brace in a 7-3 win that truly launched his Madrid career.
Ancelotti's side enjoyed less success in the return fixture, going down 2-1 in March in a game that fatally undermined their league title bid, so the reunion in the Welsh capital will also offer an opportunity for revenge.
Sevilla beat Benfica on penalties in the Europa League final in Turin to win the competition for the third time in nine seasons.
They have lost influential Croatian playmaker Ivan Rakitic to Barcelona, while Stephane Mbia -- scorer of a decisive injury-time goal against Valencia in the Europa League semi-finals -- has returned to parent club Queens Park Rangers.
But Spanish forward Iago Aspas could make his debut against Madrid, having joined from Liverpool on a season-long loan.
Coach Unai Emery has dismissed suggestions that the comparative lack of World Cup players in his squad will give Sevilla an advantage, but he has backed his team to pull off an upset.
"How can we possibly be favourites against Real Madrid" he said.
"They haven't had much time to train and won't be at their best level, but that doesn't make them not favourites.
"It is clear, though, that we have the capabilities and resources to enjoy a great final and win it."