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You can print DC only and pay postage at the PO. You pay the .27 fee to PBS to be able to print the PBS DC. Then when you pay postage at the PO you pay an additional .18 (intead of the .75 for PO DC).
If you use it with PBS DC then all the fees and postage are paid for at that time. I think the total PBS fee is .43 with printable postage.
As an example, a less than 1 lb Media Mail package would be:
No DC, no PBS Postage: $2.23 at the PO
PBS DC, no PBS Postage: $.27 paid to PBS at printing of label + $2.41 at the PO
PBS poastage (DC is required): $2.84 (2.23+.18+.43) paid to PBS at printing of label and its all ready to go