According to the Federal Police report, 44 homes and businesses were searched, netting the arrests as well as weapons, ammunition and drugs. Also confiscated were counterfeit passports, travel visas, driver's licences, and cash.
Around €55,000 in cash was also recovered.
"(This ring) was not about aiding people to flee. Everything they were doing was to make money from other people," said Federal Police President Dieter Romann in a statement released on Thursday.
Romann also said that in the last year, around 2,100 smugglers had been arrested, which led to Wednesday night's raids.
More than 500 police took part in the raids across Germany in Berlin, Hamburg, North Rhine-Westphalia, Bavaria and others.
Romann also said that further raids were carried out in the Netherlands and Belgium by Europol in connection with the smuggling ring.