Illustrative example
One spouse is asked to sign an agreement waiving support entirely. They have no earnings of their own, a long-standing health condition and no realistic prospect of work.
The prohibition is narrower than it first reads. What cannot be done is to relieve a spouse of the liability to support the other in such a manner that the other becomes incapable of self-support and is therefore likely to become a public charge; agreements about maintenance and property are permitted by Domestic Relations Law § 236, to which the opening words defer. It turns on the effect of the waiver on that spouse's ability to support themselves, not on the fact that a waiver was asked for.
They replace the blanket waiver with a modest fixed sum for a defined number of years, which both of them prefer to a clause either could attack later.