Police launched operations against the network in Ceuta, a Spanish territory in north Africa.
"We have broken up a network responsible for sending combatants to Al-Qaeda-linked terrorist groups operating in Syria," the Spanish interior ministry said in a statement.
The network, operating in Ceuta and the neighbouring Moroccan town of Fnideq, sent dozens of Islamist militants -- some minors -- to Syria, the ministry said.
"Some of them would have carried out suicide attacks while others would have been incorporated into training camps prior to carrying out armed action," the government said.
Security forces confirmed that several "jihadists" were waiting to travel from Spain to Syria, it said.
Spain's police had investigated the network since 2009 and the military-linked Civil Guard since 2011 before they joined forces early this year.
The eight suspects faced charges of belonging to a terrorist organisation, the government said.
A National Court judge supervising the investigation had issued search warrants that were being executed today, it said.
While dozens of would-be jihadist fighters have left for theatres such as Afghanistan or Pakistan in the past, Europe is facing a larger problem with Syria which is easier and cheaper to reach.
A recent report by King's College London has said up to 600 people from 14 European countries, including Austria, Britain, Germany, Spain and Sweden had taken part in the Syria conflict since it began in March 2011.
Rebel forces in Syria have asked friendly nations for anti-tank and anti-air missiles to fight back after an onslaught by government forces which have retaken key areas of the country.
The fighting has claimed some 93,000 lives and shows no sign of abating.
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