The raid was announced by Venezuelan Interior Minister Diosdado Cabello on state-controlled TV on Saturday. According to Cabello, the six individuals were part of a CIA-led plot aimed at overthrowing Venezuela's government and liquidating several of its leaders.
On Sunday, the Foreign Ministry in Madrid denied any Spanish involvement in the alleged plans to destabilize Venezuela.
The US State Department has also rejected the claims, describing them as "categorically false". The US confirms that one person working for the country's military has been detained and states that it has received unconfirmed reports that two more American citizens have been arrested.
The raid comes after the US decision to sanction 16 officials with ties to Maduro due to suspected fraud in the July election.
The EU, US, UN, and several of Venezuela's neighboring countries have questioned Maduro's claim to victory due to the lack of full disclosure of election data.