WordPress.com does not bill by invoice or purchase order.
Below are the only accepted means of payment.
WordPress.com uses PayPal as the payment processor, and as such, can only accept payment from countries they support: https://www.paypal.com/worldwide/
If for whatever reason, they have chosen to block payment from your country, you will not be able to purchase an upgrade here unless you have a source of payment outside of your country. Note: You can buy a prepaid credit card from an approved country or pay in Bitcoin.
In addition to major credit cards Mastercard, VISA, American Express, Discover, and PayPal https://www.paypal.com/worldwide/ WordPress.com can accept echecks and some debit cards.
The debit card must have a VISA or Mastercard symbol on it, and should work just like a credit card when selecting the VISA or Mastercard option on the payment form, even though it's a debit card.
More about echecks here:
WordPress.com also accept Bitcoin for payment of certain upgrades http://en.support.wordpress.com/?s=bitcoin