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I'd be interested to find out as well. We will be walking from Coimbra to Santiago next month and are trying to find a service that will transfer a suitcase from Coimbra directly to Santiago before we start walking.
We are arriving from Paris and taking the 14:52 train from Bayonne, you can get there from Biarritz on a 13:52 TGV (possibly earlier trains as well, check www.sncf.com for the options). There is another train from Bayonne to SJPdP later at 21:10 according to the website.
According to the Express Bourricot website, I would say you pay in advance at their office when you get there, and not in Santiago, but best contact them and ask. In any case you will need to get to their office to set up the transfer so I'm sure they will explain it there.
Prices and payment...
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