Club-mate Diego Llorente has been selected, though, ahead of Spain's most capped player, Sergio Ramos
The omissions are particularly brutal because coach Luis Enrique has chosen to name only 24 players, with 26 allowed.
For the first time in Spain's history there are no Real Madrid players in the squad, and Kepa Arrizabalaga, Sergi Roberto, Sergio Reguilon, Hector Bellerin, Jesus Navas, Iago Aspas, Dani Carvajal and Dani Ceballos are others overlooked.
"I've not included Ramos because he's not been able to play much this season, especially since January he's not been fit enough, and at times not even training with the group at his club," said Enrique.
"It wasn't easy, but I called him last night (Sunday) and we had a difficult and tough conversation. I feel bad as he's a player who has always been at the top level and has a future with the national team."
Rodrigo has had a difficult first season at Leeds since joining from Valencia for £27m, but finished it strongly.
Leeds coach Marcelo Bielsa is very particular about making players, particularly attacking ones, learn his way of playing before throwing them into the action and although Moreno had Premier League experience, it was with Bolton Wanderers a decade earlier.
He therefore started out of the side and in his place, Patrick Bamford made a terrific start to the season, so much so that when Rodrigo broke in, it was in a deeper position than he was used to.
Just as he was finding his feet, scoring an equaliser at home to Manchester City, he contracted coronavirus in October.
Bielsa is of the view that Rodrigo more than most needs the rhythm of games to find his form, but 10 consecutive starts either side of the turn of the year were ended by a groin injury at Leicester City in January.
He was just coming back to form at the end of the season, and was even being used at times in the No 9 position where he normally performs for Spain, but it appears to have been too little, too late.
Alvaro Morata, Mikel Oyarzabal, Gerard Moreno, Dani Olmo, Pedri, Pablo Sarabia and Manchester City's Ferran Torres and Adama Traore, formerly of Middlesbrough, now with Wolverhampton Wanderers have been preferred for the forward positions.
The biggest call has been to omit 180-capped Real Madrid captain Ramos, and Llorente has been one of the defenders chosen instead.
Llorente also arrived in the summer to add top-level quality to newly-promoted Leeds but struggled with a succession of muscle injuries, making two appearances before his first ful 90 minutes came at the end of February. He followed that with 13 consecutive starts, broken only by a minor muscle problem during the penultimate game of the season at Southampton.
His assured defending and composed passing brought a new dimension to the Whites, confining German international Robin Koch to the bench when he recovered from injury.
He tweeted of his "happiness", "pride", "responsibility", "satisfaction" and "gratitude" at his selection.
Other Premier League players included are David de Gea, Robert Sanchez, Aymeric Laporte, Eric Garcia, Thiago, Rodri and to the surprise of many, Cesar Azpilicueta.
Spain are in a group with Sweden, Slovakia and Mateusz Klich's Poland.
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