Nineteen works were stolen from the private collection of Spanish billionaire Esther Koplowitz's luxury apartment in the upmarket neighbourhood of Chamartin while she was on holiday.
Among the paintings taken in August last year were two by Spanish artist Francisco de Goya - The Donkey's Fall and The Swing - and a work by French impressionist Camille Pisarro, called Eragny Landscape.
Police recovered 10 works in total, nine of which were found in the boot of a car after an officer posed as an American interested in buying Pieter Brueghel's The Temptations of St Antonio for one million euros (£646,000).
Police said Juan Manuel Candela and Angel Suarez Flores, both of whom have past criminal records for robbery, were arrested in the hotel where the rendezvous took place.
Luis Miguel de Mazo, a security guard at the apartment, originally told police the robbers got into the apartment by assaulting him after he answered the door. But Mr De Mazo gave himself up to police after the arrests were made.
FBI expert
Among the works recovered were The Swing, Tsuguharu Foujita's Child with Hat, Pisarro's masterpiece and the Pieter Brueghel work, all of them in a good state, police said.
Police chief Juan Cotino said in a news conference that the arrests were made after two undercover policemen met the suspects about the Brueghel.
As soon as the painting's identity was confirmed by an FBI expert posing as an art professor, the pair were arrested.
Police then found the other nine paintings in the car parked near a football stadium, but are still working to recover the remainder of the stolen collection.
"It's the most important art seizure in the last decade internationally, both for its artistic and economic value," Mr Cotino said.
A robbery charge carries a maximum sentence of five years imprisonment in Spain.
Spain's wealthiest
Ms Koplowitz, 52, holds a 56% stake in Fomento de Construcciones y Contratas, Spain's biggest construction company with turnover of £2.46bn.
Forbes magazine listed Ms Koplowitz as the 445th richest person in the world this year, with an estimated wealth of £665m.
She and her sister Alicia are Spain's wealthiest women.
At the time of the robbery last year, police believed the theft must have been ordered by a wealthy collector as the pieces were too well-known to be sold easily.
And they immediately suspected some form of inside job since the paintings were piled in a single room at the house which was undergoing construction work at the time.