For your wife's company to opt out of MA PFML, they need to have an alternate option (insurance based or company paid) approved by the state. Since this could negatively affect new employees that would otherwise qualify for MA PFML, most alternate options should have a provision that includes newer employees. I had a new coworker that did this. The private insurance plan based her benefit amount on her prior income.

As long as your wife would have qualified for MA PFML, her company should be required to offer her something. She needs to go back to HR and ask for information on their family leave plan. She can also go directly to MA PFML and explain what's going on. Either her employer is doing something wrong and MA PFML needs to know or they are misguided.

To answer your title questions, you need to talk to your HR. You likely qualify for both if you've been working at that company for at least a year and pay into PFML.