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Leon is best accessed by bus or train; it is poorly connected by air. EasyJet goes from Edinburgh to Madrid. Renfe trains Madrid to Leon vary from 2.5 to 4.5 hours but service is frequent. Alsa operates buses direct from T4 Barajas airport (MAD) to Leon that take about 5 hours.
Renfe
http://www.renfe.com/EN/viajeros/index.html
Alsa
http://www.alsa.es/en/buy-and-schedules/national/?searchType=common
There are other airports that might work. There are lots of buses and trains that will connect; the problem will be frequency of flights. Here is Aena airport network.
http://www.aena-aeropuertos.es/csee...s/en/Page/1237548207921//Airport-Network.html