Unfortunately the shipping label charges usually take a few days to show up, most times they do come out of pending funds but sometimes the funds are released (paid) before the label charges show up. If that's the case it will come from your bank account, or if you've sold more items against the next pending funds.
If you look at your payment summary they will show there as a negative once they have been charged. Note that if you haven't sold for a while your funds will probably be on hold longer than usual and the shipping charges will probably come from pending in that case. Once you've received your money (pending funds) and if you still owe for the labels eBay sends an email letting you know they will be taking the funds from your bank by....(a date usually about 4 business days away).
Ideally the label charge should come out right away from the pending funds but that doesn't always jive time wise. In my case most times the label funds end up coming out of my next sale, not always the ones related to the charge.
