TORFAEN MP Paul Murphy said Pete Hain was "an excellent Minister and a strong voice for Wales in Government.
Murphy was Peter Hain's predecessor as both Welsh and Northern Ireland Secretary.
He said: "I am very sorry to hear that Peter has resigned.
Don Touhig, MP for Islwyn, said of Peter Hain's resignation: "I'm very sorry to hear the news. Peter Hain was an excellent Secretary of State."
Murphy added: "He deserves particular recognition for his good work in helping bring the Northern Ireland peace process to a successful conclusion.
He also stated: "I'm sure he'll continue to work hard for his constituents from the backbenches."
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