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I also have opened a Nationwide account and also have one of their Visa cards. I have paid in £1000 to my flexi account and will draw on that when I get to Spain on Saturday.
I find using the ATMs is very easy, as long as I remember to make sure they have an English translation on them. I do get confused sometimes because they often put up a message about charging in euros or sterling and I'm not sure really what they mean. Can anyone help on that?
I keep around 50 euros back at the end of each trip to use when I arrive next time to tide me over until I get to an ATM.
If I need to buy euros before I go I always use the Post Office, convenient and commission free.