The Brazilian was pulled over on the afternoon of February 12 on the M-12 highway and it was discovered he had previously been stripped of all his points, rendering his licence invalid, the authorities said.
Marcelo is the latest Real player to fall foul of Spain's traffic laws after their France striker Karim Benzema was clocked driving at 216 kph in the early hours of February 3, more than twice the speed limit of 100 kph.
The 25-year-old faces losing his licence as well as a possible fine, a period of community service or even a short prison sentence, according to Spanish law.
The two incidents, as well as recent transgressions by other high-profile players including former Germany captain Michael Ballack, have drawn criticism from a Spanish association which supports victims of traffic accidents.
The "STOP accidentes" group criticised Real captain Iker Casillas for driving with a cast on his injured hand and Barcelona defender Gerard Pique for carrying his infant son in the front seat without the proper safety equipment.
"Many players are persistently breaking traffic laws and they are people with a significant influence on the majority of the population, especially young people," the association said in a statement on their website (stopaccidentes.org) on Tuesday.
They added that they had written to all 20 of Spain's top-flight clubs and the professional league urging them to join a campaign to raise traffic safety awareness.