The case follows a four-year investigation into claims of embezzlement, false accounting, tax fraud and money laundering in television rights deals between 1994 and 1999.
Berlusconi, a flamboyant showman who defied national opinion and backed US President George W Bush's war in Iraq, could face up to six years in jail for tax fraud if convicted.
The 69-year-old has managed to avoid jail in at least seven previous graft trials.
He was found guilty four times, but verdicts were overturned on appeal or the statute of
limitations applied and charges were dropped.
The decision to go to trial follows Berlusconi's defeat in April elections, which saw Italy's longest-serving post-war prime minister ousted from power in what he angrily claimed was a fraudulent result.
He has repeatedly accused magistrates of working on behalf of the centre-left and said they would pursue him if he lost power.
"It was a predictable decision, considering the previous hearings in Milan," said Mr Berlusconi's lawyer Niccolo Ghedini after today's ruling. "They haven't allowed crucial witnesses for the defence to be heard."
Among the 13 people also ordered to stand trial was British lawyer David Mills, estranged husband of a British government minister, and Mediaset chairman Fedele Confalonieri, judicial and legal sources said.
For two of the 13, the statute of limitations applies, meaning they will not be tried.
Mediaset, in a statement, denied any crimes and said its executives and directors had always acted correctly.
Prosecutors suspect a US firm sold television and cinema rights to two offshore firms controlled by a Berlusconi family holding company, Fininvest.
The offshore firms then allegedly inflated the prices and sold them to Mediaset, controlled by Fininvest, to avoid Italian taxes and create a slush fund.
In a related case, Milan prosecutors have accused Mr Berlusconi of paying Mr Mills a kickback of $A805,000 for not revealing details of his media empire when Mr Mills testified in two court cases.
Mr Mills told Britain's Channel 4 news he was innocent and said the case had nothing to do with his wife, Britain’s Culture Secretary Tessa Jowell.