Sorry, no. She can't make contributions to an HSA unless she is (1) enrolled in an HSA-eligible HDHP plan, and (2) has no other health insurance coverage. (It doesn't matter that you say you plan to not make any claims -- the coverage exists, therefore she would be ineligible to contribute to an HSA.)
It's not the insurance company you have to worry about, it's the IRS. (Although she probably will have to sign a statement certifying to her employer that she has no other insurance coverage in order to get the match.) You have to certify on your (joint) tax return that she is covered by an HSA-eligible plan and has no other insurance coverage. If you get caught, you owe back taxes, interest, a 20% penalty for ineligible contributions, and possibly an additional 25% penalty for knowingly filing an inaccurate tax return.
You will need to decide to continue her coverage under your employer's plan or drop her and have her covered by her employer only. Of course, she can be covered by as many policies as you want -- she can be covered by both plans, she just can't make HSA contributions.
