I'm having the same problem!!! I called PayPal help and the lady was really nice, but there was very little she could do to help. It's a security measure apparently and nobody has anyway of over riding it!!!! Mental, the machines have total control over money! I have money I've put in to my paypal that I can't spend anywhere and all us mere humans can suggest to fix this is 'to wait 24 hours and it MIGHT work then', or 'try smaller amounts like 5 pounds next time'! I was only trying to deposit 25 pounds in a betting account, hardly Mr high roller! This is a real pain as all the money I have at the moment is in paypal.
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