Zuckerberg, who has a fortune of almost $7 billion according to Forbes magazine, said in a brief statement that he signed up the initiative to provide some leadership for younger entrepreneurs.
"People wait until late in their career to give back. But why wait when there is so much to be done?"
"With a generation of younger folks who have thrived on the success of their companies, there is a big opportunity for many of us to give back earlier in our lifetime and see the impact of our philanthropic efforts."
Other notable billionaires to sign up to the initiative overnight included so-called junk bond king Michael Milken, well known activist investor Carl Ichan, the founder of investment research firm Morningstar Joe Mansueto, and Sidney Kimmel, a clothing billionaire behind such brands as Nine West and Jones New York.
Buffett and Gates have now convinced 57 billionaire families to sign up to the pledge, which is essentially a commitment to give at least 50% of their fortune away. Most will do so via their private foundations and charitable organisations, although Buffett has already given Gates about $8 billion to manage through the giant Bill & Melinda Gates foundation.
Big names to sign up early included New York Mayor Michael Bloomberg, Oracle founder Larry Ellison, Star Wars director George Lucas and US media mogul Ted Turner.
Buffett said in a statement that the Giving Pledge initiative has got the world's wealthiest thinking about charity again.
"The Giving Pledge has re-energised people thinking about philanthropy and doing things in philanthropy and I look forward to many more conversations with families who are truly fortunate, and whose generosity can and will change lives."
But there has been some criticism of the pledge, with suggestions some of the billionaires maybe be joining the initiative for PR purposes, and "recycling" previous donations and presenting them as new pledges.
There have also been suggestions that the style of philanthropy used by many billionaires – where money is often pledged to education and cultural institutions that they were previously associated with – does not really help the world's poor.
As if anticipating this, the latest Giving Pledge announcement includes a comment from well-known Australian ethicist Peter Singer, who says the initiative is "changing the culture" of philanthropy.
"Research shows that when people know that others are giving, they are themselves more likely to give. So publicly pledging to give will encourage others to give. This holds true for billionaires and for those of us who aren't anywhere near that level of wealth."
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