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There are so many travel options to get you to your start point. As others have already posted you will almost certainly need to break your journey with a couple of changes. For example, there is a coach from Santander to Oviedo, along the coast, and then a change down to Leon which is a major...
I caught the Madrid to Pamplona bus on Friday, left at 3.00pm stopping in Belorado at 6.30 pm and then Santo Domingo I think. As GerFol says above, it’s not Alsa but another bus company. You can catch it from the main bus station in Avd De America - which is on the metro.
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