You always have the right to ask unregistered guest to vacate your property. Expanding on this, it is always best to have very clearly stated rules about visitors. This way, if this happens again you have more to support yourself with when asking them to leave.
That being said, some guest really don't realize they should ask about having company over. I had a younger guest assume my room followed the standard of a hotel and she could have her boyfriend over whenever she pleased. Then I have had guest that purposely snuck people in through the garage or back doors, knowing this was not allowed.
Approach her nicely and kindly remind her that her reservation was for one person, and that at this time you do not allow unregistered guest to be on the property. If someone ever starts to protest or get angry, I remind them it is a safety/liability issue because unregistered people are not covered by airbnb policies.