One of those held is a former minister, Slobodan Milosavljevic.
Two former interior ministry officials, several serving and former mayors, and a number of executives in state-owned firms were also detained.
The move comes after Serbia opened talks to join the EU, which has long pressed Belgrade to tackle corruption.
Interior Minister Nebojsa Stefanovic said the charges for those arrested included abuse of office, money laundering and other financial crimes.
The alleged offences date back to 2004, involving the suspected embezzlement of 7.8bn dinars ($70m).
Mr Stefanovic said police were searching for five more suspects. Another 39 are under investigation.
A ministry statement said that Mr Milosavljevic was being charged with abuse of office when Minister of Agriculture, Forestry and Water Management from May 2007 to July 2008 and when head of the Chamber of Commerce, from 2004 to 2007.
Former head of the government's anti-corruption agency, Zorana Markovic, was also detained.
Many of those arrested are from the opposition Democratic Party. Its leader said the detentions were politically motivated.
Tackling corruption and organised crime will be high on the agenda of the Serbia-EU accession negotiations, which began on 14 December.
Police in Serbia have arrested about 80 people in what has been described as the country's biggest anti-corruption investigation in decades.