That's an interesting question. If you look a few threads up you'll see a thread about how Plan B works. It delays ovulation. I'm not sure how long it delays ovulation, however. You'd have to make sure it delayed ovulation long enough so that any sperm deposited in your gf's body died before ovulation (when the egg is released). Basically you don't want her egg and your sperm to meet. Your sperm can live up to 5 days (I've read some places that say sperm can live up to 7 days) while it's waiting around for ovulation, which is when the egg is released.
So, Plan B would have to delay ovulation for over a week for it to prevent the egg from meeting up with the sperm.
Also, the other way Plan B works is to thicken the mucus surrounding the cervix, which would hinder the sperm from getting to the egg. However, I don't know how long it has that effect, either.
There is also a chance that it could backfire and enhance the chances of your girlfriend getting pregnant, because Plan B is progesterone, and progesterone is the hormone the body uses to maintain the uterine lining so it is optimal for a fertilized egg to implant.
You can call 888-NOT-TO-LATE to ask these and any other questions you may have concerning emergency contraception.
Please note that the purpose of Plan B is to be used in case your primary method of contraception failed, like a condom broke, etc. It is not a primary form of contraception. The side effects are very, very unpleasant, and definitely not something you'd want to experience unless you were indeed facing an emergency situation.