Greece has flown 30 refugees to Luxembourg in the first round of relocations under the EU's plan to redistribute migrants.
The six families, from Syria and Iraq, are among the first to be moved under aims to share out nearly 160,000 migrants across the bloc. Some EU members fiercely oppose the scheme.
More than 600,000 people have arrived in Greece by sea so far this year.
Meanwhile German police have launched raids on human trafficking networks.
More than 500 officers searched homes and businesses in the states of North Rhine-Westphalia, Lower Saxony and Baden-Wuerttemberg on Wednesday morning.
Germany expects at least 800,000 asylum seekers this year - some estimates are as high as 1.5 million. That is at least four times the number who arrived last year.
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