It comes after he was booked in their win over Italy on Thursday night.
Rodri had previously been cautioned for conceding a penalty in the opening victory against Croatia.
He fouled Bruno Petkovic inside the area, although a VAR review opted against upgrading the sanction to a red card.
However, Rodri will still serve a ban during the group game with Uefa rules implementing a one-match suspension for two yellow cards
The manner of his second booking of the tournament is also down to a new Uefa rule introduced for the tournament.
In a bid to ease the pressure on officials, only captains are allowed to speak to referees.
Any other player will be booked if they approach the referee whilst showing any signs of dissent.
Rodri was cautioned by Slovenian referee Slavko Vincic against Italy after confronting the official.
Striker Alvaro Morata is the Spain captain at this summer’s Euros in Germany.
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During that time, Spain have played nine matches, losing just one inside 90 minutes.
City star Rodri had started both the wins over Croatia and Italy, which have booked Spain’s place in the knockout stages.
Already confirmed as group winners, the three-time champions will face a best third place team in the last 16 on June 30.
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