Yes, you can marry her, and yes it will be valid in the US. Your last question requires more information to answer-- how long out of status?
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How long would she have been out of status at the time of marriage?
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You can immediate.y marry. Whether she can apply for COS in the US to H-4 will depend on how long she is out of status.
Behar Intl. Counsel 619.234.5962 Kindly be advised that the answer above is only general in nature cannot be construed as legal advice, given that not enough facts are known. It is your responsibility to retain a lawyer to analyze the facts specific to your particular situation in order to give you specific advice. Specific answers will require cognizance of all pertinent facts about your case. Any answers offered on Avvo are of a general nature only, and are not meant to create an attorney-client relationship.
She is not out of status even technically until she divorces, if she wants to change her status without leaving the USA, make sure you marry her very soon (like the next day) and on the day of new marriage file the COS I-539.
Legality of your marriage will not be affected by the immigration status. You should file change of status ASAP. Best Wishes!
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Contact (317) 660-6174 for specific legal advice. Answers here are not legal advice because they are of general nature and not tailored to your specific situation. You should not act on this answer without checking with an Immigration Attorney.