The women, allegedly lured with the promise of good jobs in Europe, were first flown to Mexico or Brazil, travelling on false identity documents.
From there, they were flown to Paris, then smuggled into Spain to work in the sex trade, police say.
Five women who were victims of the sex ring were freed in the raids.
Police found one member of the gang performing an abortion on one of the five women, reports the BBC.
Arrests were made across Spain – in Madrid, Toledo, Cantabria and Palma de Mallorca.
More than 100 vans concealing luxury goods were also seized.
The gang used the vans to launder their profits and send them back to Lagos, police say.
The vans, with dark-tinted windows and welded doors, were stocked full of beer but had luxury items hidden deeper inside.
Goods worth an estimated 5m euros (£4.1m; $6.6m) were found in 94 vans seized in Madrid and another 26 in the port of Valencia, including high-end televisions and cases of alcohol.
Police say the gang was formed more than 20 years ago in Nigerian universities and was also known for sending so-called Nigerian letters by email, asking recipients to send money.
They should all rot in jail.
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