Doctor Explosión sing both in english and spanish. Probably the best live spanish band in their style since the early 90's. They have some pretty cool albums, some of them recorded at Toe Rag. Their leader Jorge has this cool studio: http://www.circoperrotti.com/home.html
From the 80's, Los Negativos were the faves among the Garage-psych-mod crowd, with a classic debut album from 1986, 'Piknik Caleidoscópico', one of the highest rated ever 60's styled spanish albums.
From the 60's, my faves are Los Cheyenes, Barcelona's own Pretty Things, early Kinks and dutch Outsiders all in one. Wilder than the (otherwise excellent) Los Salvajes. In a more Beat mood, some stuff by Madrid's Los Brincos is also top class. Los Cheyenes and Los Brincos have been covered in past issues of 'Ugly Things'.
Here's Los Cheyenes:

I've been told the new Wau y los Arrrghs album is awesome, but I haven't heard it yet. And add Los Fumestones to the list, too!