If the alimony was set by a voluntary agreement or settlement that he and his then-wife voluntarily entered into, it can only be changed if she agrees to the change; if she does agree, they can simply both sign an amendment to the settlement agreement and file it in court. What was agreed to volutarily between two parties can be changed voluntarily by them. If she does not agree, however, he cannot force the change.
If the alimony was set by a judge in a court order or judgment or decree, he'd have to apply to the court (e.g. make a motion) for the change. If his ex will sign something that she does not oppose the change, it is very likely be granted; if she does oppose, he'd have to convince a judge to give it to him over her objections. What was determined by a court can only be changed by a court.
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