Is it possible to add additional dictionaries to the dictionary application?

The English one works fine, but the one under preferences called ‘Spanish Dictionaries’ does not seem to work. Is it possible to add one for Spanish that works? I’ve not been able to find one yet.

I didn’t use that one, don’t know how to add additional dictionaries, sorry. But I can recommend you ‘Goldendict’ (in Ubuntu Software Center). Download dictionaries here:
Spanish dictionaries (bgl files) here or here
Diccionario de la RAE (dz file) here
Other dictionaries here and here