Your mother needs to schedule an in person confidential meeting with a practicing attorney as several crucial issues must be properly explained to her on legal options. I may recommend Counsel Alexander Segal.
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She should be able to adjust status even though she entered on the VWP and overstayed, so long as she is not the subject of an INA section 217 removal order. You should strongly consider using a lawyer for a matter this important. It's not worth the risk to attempt this without a lawyer. The character of the person she married will not affect her ability to become a Lawful Permanent Resident.
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Your mother needs to consult an immigration attorney. The fact that she overstayed from the visa waiver program could pose a problem.
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