On PAYG you are not billed. So EE would have no reason to take money out the blue. Have you set up a recurring DD top-up that you have forgotten about, maybe? Otherwise if it was an unexpected DD that you were not notified about in advance, you may use the bank's DD Guarantee to reverse the payment.
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To phone EE: The local rate landline number +44 207 362 0200 or Freephone +44 800 079 8586 - Option 1 for Mobiles; Option 2 for 4G WiFi; Option 3 for Home Broadband & EE TV.
ISPs: 1999: Freeserve 48K Dial-Up => 2005: Wanadoo 1 Meg BB => 2007: Orange 2 Meg BB => 2008: Orange 8 Meg LLU => 2010: Orange 16 Meg LLU => 2011: Orange 20 Meg WBC => 2014: EE 20 Meg WBC