Police seized 575 kilograms (1,270 pounds) of the drug and closed five secret laboratories in a global swoop together with US, Brazilian and French police.
They also seized 11 firearms including an assault rifle along with €588,000 ($765,000) and $7 million in cash, the Spanish police said in a statement.
The alleged head of the ring, which moved drugs and cash between South America and Europe, was a "known Colombian drug dealer" living in Brazil, who was arrested in Rio de Janeiro, the police said.
The cocaine was sent to Spain and transferred to five laboratories in Malaga, Madrid and Cordoba to be cut and then sold in Spain, France and Italy.
It was transported in false bottoms in the bodies of cars.
Two of the cars were seized in Marseille, southern France, one of which was carrying 30 kilograms of cocaine.
Police detained 70 men and four women, including Spaniards, Colombians, Portuguese, Iranians and Bolivians.