Using the pill and VCF together should be VERY effective at preventing pregnancy. The pill alone, if used perfectly, has about a 99% effectiveness rate, and using the film on top of that will just make it that much more effective.
Nothing is ever 100% of course, but using two effective contraceptive methods together (correctly) is probably about the closest you will get to 100%, barring abstinence. They do not protect against STDs, however; condoms would be better for that. Also, pulling out is really quite pointless; it achieves nothing.
If she is good and consistent with her pills and is using the film properly, you should be well protected indeed!