Over at Air Transat it looks like they've got flights from Montreal/Toronto to Porto and Lisbon as well as Toronto to Faro and Ponta Delgada. I don't see them loaded on exit.ca however.

As for Spain, the only Canadian charter would be Skyservice into Palma De Mallorca (which is not on the mainland). Royal used to do Malaga and Madrid but that died along with Canada 3. Looks like Spanish charter Air Plus Comet is doing Saturday flights from Toronto to Malaga, which, based on this review is an effective way to smuggle things into Europe