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So. I made an accidental purchase on PSN for a hefty fee(£58) and am wondering if there is anything I can do to get it refunded. Any excuse or reason is helpful right now.

I would suggest using the Sony Support Forums for that question. They'd be far better-equipped to answer those questions than we would.

Though, digital purchases don't often have a return policy, what with the many resources available to copy and transfer them. Still, that's just a guess, Sony would be a far better resource.

From the google:

"Re: ACCIDENTAL PURCHASES and DOWNLOADS from PS Store
OPTIONS
Oct 31, 2010
Regardless of policy, Sony Cust Care can assist you. This happened to me a long while ago when I purchased Destruction Derby. I was issued a refund. Call 800-345-SONY. Not all reps will assist. Be persistent."

 pretre wrote:
From the google:

"Re: ACCIDENTAL PURCHASES and DOWNLOADS from PS Store
OPTIONS
Oct 31, 2010
Regardless of policy, Sony Cust Care can assist you. This happened to me a long while ago when I purchased Destruction Derby. I was issued a refund. Call 800-345-SONY. Not all reps will assist. Be persistent."

Is that a US number?

It's a toll-free US number, yes but, I would imagine that, were you to go to the Sony Playstation Support website:

http://bfy.tw/1dup

You could find a phone number or email by which you could contact Sony.

I have emailed them and I'm waiting on a response.