Goalkeeper Iker Casillas and playmaker Xavi, who helped Spain win the tournament in Nigeria 14 years ago, reached 150 and 127 caps respectively in Friday's 2-0 World Cup qualification victory against Finland in Helsinki.
Casillas drew level with former Germany midfielder Lothar Matthaeus in 12th place on the all-time list, while Xavi climbed to second on Spain's appearances ranking above former keeper Andoni Zubizarreta.
Casillas and Xavi play for bitter rivals Real Madrid and Barcelona but have remained firm friends and have been key performers during Spain's glittering run since their triumph at Euro 2008.
At Euro 2012 last year, they became the only nation to win consecutive European crowns with a World Cup in between and along with the hosts will be among the favourites at the World Cup finals in Brazil next year.
Xavi, 33, remains a fixture for Barca but the 32-year-old Casillas is going through something of a crisis at Real after losing his place in the starting lineup under Jose Mourinho last season.
Mourinho's successor Carlo Ancelotti has left him on the bench in Real's opening three La Liga matches, opting to stick with Diego Lopez, who was bought from Sevilla as cover when Casillas broke a bone in his hand in January.
Spain coach Vicente del Bosque, who was in charge at Real between 1999 and 2003, has firmly backed his captain and included him in Helsinki on Friday even with Barca keeper Victor Valdes on excellent form.
The defensive-minded Finns barely tested Casillas but he responded well to the sole moment of real danger, saving with his legs when the ball ricocheted off Sergio Ramos towards goal in the 12th minute.
Del Bosque said he had been more concerned about how to break down Finland's defence than who would play in goal.
Any one of Spain's three keepers - Casillas, Valdes and Napoli's Pepe Reina - was perfectly capable of playing, he told reporters.
"At this stage of the season it's not a problem that Iker hasn't played," he said.
"He comes from a pre-season during which he had minutes on the pitch, he is working well in training and he was at an excellent level in our latest sessions. We will see what happens in the future."
Speaking to Spanish radio about the keeper situation in the run-up to the Finland game, Del Bosque suggested Casillas had lost his starting place at his club because of his role in trying to ease tension between Spain's Real and Barca players.
Several "Clasicos" in recent years were marred by brawling, accusations of refereeing bias and play-acting and Del Bosque said Casillas had played an important part in making sure the national team was not seriously affected.
"We are obliged to remember some things and we cannot forget what happened because they were difficult moments for the national team and Iker helped a great deal," he said.
Spain's comfortable victory in Finland means they have a three-point lead over France at the top of qualification Group I with two of eight matches left.
They play their final two games at home to Belarus and Georgia next month.