A spokesman for the Interior Ministry said the man had returned to Spain from Syria where he was trained by fighters from al-Qaeda off-shoot al-Nusra but fell out with his mentors and joined ISIS.
According to investigators, the suspect was in charge of radicalising and recruiting young people in the Tolosaldea region of Spain.
He has been targeting disaffected teenagers, preferably of Moroccan origin, and forging close relationships with them.
They said they were aware of at least one young Spanish-Moroccan man travelling to Syria with the suspect in 2013 where both received firearms training.
The recruited was killed in the Syrian-Iraqi conflict zone two years later.
His family said prior to his radicalisation he was a young man with no religious background and was not radical.
Investigators said she carried out propaganda work through social networks, where she used very aggressive slogans, jihadist emblems and published extremely violent videos edited by herself showing a radical Islamist ideology in favour of the Palestinian cause.
She collaborated with the ISIS through a contact she had with a well-known recruiter in Syria.
She had gone through all the necessary procedures to move with her four children to the conflict zone to meet her ISIS fighter husband who travelled there in 2014 and held a senior position with the extremist group.
Police said she had a deep hatred for Western culture and transmitted it directly to her children.
In her daily life she used important security measures to avoid being detected, especially after her husband left in 2014, when his name appeared in some media.
Spain has arrested 190 suspected jihadists since 2015 when the Interior Ministry raised the Anti-Terrorism Alert Level to 4.