"By accelerating this boost to developing countries market access, the European Union has acted quickly to provide relief for countries affected by the recent tsunami," Trade Commissioner Peter Mandelson said in statement.
"By lowering tariffs for poorer countries, we are extending benefits to all developing countries," he added.
EU countries agreed on January 28 to bring forward the application of the bloc's "Generalised System of Preferences" (GSP) to April 1, in advance of the scheme's planned introduction on July 1.
The new scheme, which was prepared by the previous commission, simplifies a previous preferential trade regime.
The commission estimated that concessions on tariffs under the new regime would would boost trade flows with the tsunami-hit countries by three billion euros (3.9 billion dollars), mainly for fish products and textiles.
Sri Lanka is set to be the main beneficiary of the scheme, under which 90 percent of the South Asian country's exports to the EU will be tariff-free.
Thailand would benefit from a reduction to 4.2 percent, from 12 percent, on its lucrative shrimp exports to Europe. India and Indonesia would gain from better terms on their textile and shoes exports.
British charity Oxfam welcomed the move, but warned that more action was needed.
"The European Commissions decision to bring forward a new system of trade preferences for poor countries will help reduce poverty by improving market access, but the gains will be limited as many protectionist measures persist," the aid agency said in a statement.
More than 284,000 are people are believed to have been killed in December's tsunami disaster.