I am assuming the medication she was on for her skin was an antibiotic?
There is a possibility that antibiotics can decrease the effectiveness of the pill in some women. However, women who use antibiotics as a treatment for acne, etc, and use it long term (more than 3 weeks) should experience no decrease in efficacy. This is because there is a possibility that the antibiotic could cause the gut flora to break down, which means the pill may not be absorbed properly. 3 weeks allows the gut flora to build back up, and normal pill absorption to return.
If your girlfriend had been using the antibiotic for under 3 weeks, there is a possibility, however a very slim one, that this could have effected her pill. There is only one proven antibiotic that decreases pill efficacy and it is rifampin; most clinical studies have shown no link between more widely prescribed antibiotics, such as those taken for one's skin, and loss of pill efficacy. However, in the real world, many people have attributed pill failure to a course of antibiotic treatment. Nevertheless, Plan B was a good idea as a back-up precaution. Plan B is very effective; so IF in the VERY SLIGHT possibility your girlfriend was one of those rare cases where her body's absorption of the pill could have been effected, you did the right think in taking Plan B at the right time.
I highly doubt you have anything to worry about, but best of luck.