Yes! Upon payment you will receive a confirmation email with the billing details.
Also, you can view the payment confirmation for any orders placed after July 2015 in your Account settings. To access the page:
1. Click the arrow next to your username in the upper right of edx.org
2. Select Account.
3. In the middle of the Account Settings page click Order History.
4. Click Order Details to view the confirmation page of an order.
If you have paid by PayPal you can also find a detailed invoice within your PayPal account.