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As you may know, 20 Pa. C.S. § 6111.2 states:
If a person domiciled in this Commonwealth at the time of his death is divorced from the bonds of matrimony after designating his spouse as beneficiary of a life insurance policy, annuity contract, pension or profit-sharing plan or other contractual arrangement providing for payments to his spouse, any designation in favor of his former spouse which was revocable by him after the divorce shall become ineffective for all purposes and shall be construed as if such former spouse had predeceased him unless it appears from the wording of the designation, a court order or a written contract between the person and such former spouse that the designation was intended to survive the divorce. Unless restrained by court order, no insurance company, pension or profit-sharing plan trustee or other obligor shall be liable for making payments to a former spouse which would have been proper in the absence of this section. Any former spouse to whom payment is made shall be answerable to anyone prejudiced by the payment.
In order to prevail, you would have to show that your ex-wife intended to leave you on. Evidence may be documents showing where she renewed the plan after the divorce and left you on there, etc.
I suggest that you get the proposed document he wants you to sign off on and then go see an attorney of your own before signing it. There are always exceptions to the rule, and if you can produce some evidence of her intent, you may be entitled to the 401k money.
Feel free to ask any follow-ups.