Federal police officers armed with 29 arrest warrants and more than 100 search and seizure orders carried out the operation in eight states and the Brasilia federal district.
They targeted those involved in the "illegal extraction, exploitation and trade of wood" as well as corrupt officials inside environmental protection agencies and timber companies, police said in a statement.
Some 50 million reais (US$12 million) belonging to companies under investigation were also frozen.
A former employee of the Brazilian Institute of Environment and Renewable Resources was among 19 people arrested, a federal police spokesman told AFP.
The investigation that led to Thursday's raids had already resulted in the seizure of 400 containers holding 8,000 cubic meters of wood in December 2017 in the river port of Manaus, the main city of the Amazon.
The illegal shipment included "140 containers for export to countries in Europe, Asia and North America," the police statement said.
The raids come as thousands of Indigenous people from across the country stage an annual three-day protest in the capital to defend hard-won land rights they fear could be eroded by far-right President Jair Bolsonaro, a champion of mining and agribusiness, who took power on Jan. 1.
Their concerns were reinforced Thursday by a global report showing that an expanse of tropical forest nearly the size of England was destroyed in 2018, a quarter of it in Brazil, home to around 60 percent of the Amazon rainforest.
Nearly a third of primary forest destruction in the world took place in Brazil (13,500 square kilometers, 5,200 square miles), according to the annual assessment from scientists at Global Forest Watch (GFW).
Amid growing tensions over the Amazon, a separate report Thursday accused companies in Europe and North America of "complicity" in the destruction of the rainforest by trading with and investing in Brazilian companies linked to illegal deforestation.
"If they continue to support Brazilian companies, they should be ready to shoulder the blame for the destruction of rainforests and the abuse of indigenous peoples," said U.S. activist group Amazon Watch.