Greece will begin the process of sending refugees, mostly Syrians and Iraqis, to other EU member states under the bloc's refugee relocation plan on Wednesday (local time).
Greek Prime Minister Alexis Tsipras will meet a first group of 30 refugees at Athens airport early on Wednesday morning before they voluntarily board a plane for Luxembourg, the government said in a statement on Tuesday.
The European commissioner for immigration, Dimitris Avramopoulos of Greece, as well as European Parliament president Martin Schulz and Luxembourg Foreign Minister Jean Asselborn will attend the launch of the program, an EU statement said.
Under the EU plan, nearly 160,000 migrants, including 66,000 for whom Greece was the first port of call, are to be shared out among EU countries after being processed at so-called "hotspots" in Italy and Greece.
On Thursday, Schulz and Tsipras plan to travel to the Greek island of Lesbos, where thousands of migrants arrive each day from nearby Turkey.
More than 200,000 migrants arrived in Greece in October alone, according to the UN refugee agency, though many have moved on to other EU states.
Last week, at least 80 refugees including many children drowned off Lesbos and other Greek islands following shipwrecks caused mainly by poor weather.
Despite sometimes violent winds, refugees continue to flock to Greece with hopes of travelling on to EU countries further north while fearing that more and more border closures will block their progress.
Some EU member states such as the Czech Republic, Hungary, Slovakia and Poland oppose the mandatory quota plan for refugee relocation.
A group of conservatives parties from across Europe met recently in Madrid and called for a strengthening of the union's external borders.
European Commission chief Jean-Claude Juncker last week called on member states to abide by the "relocation" plan and do more to accommodate migrants.