The suspects, aged from 20 to 72, are accused of seeking contact with children via an online social network last September. After performing sexual acts during video chat, they demanded the minors do the same.
Jörg-Uwe Hahn, state justice minister of Hesse, said the police had searched the apartments of some 40 individuals in Hesse, Bavaria, Mecklenburg-Western Pomerania and North Rhine-Westphalia starting last week.
Many are thought to have used social networks to abuse children in other cases.
The massive investigation, led by Frankfurt's top prosecutor, involved 130 police officers.
Hahn called the internet "the world's biggest crime scene," but said "this current strike against child abusers shows there is nowhere to hide from the law."