They also banned the purchase of gold, precious metals and diamonds from the country, and banned Syrian cargo flights from the European Union.
The EU had previously imposed several rounds of sanctions on Syria, freezing the assets of 100 people and 38 organizations, and trying to cut the country's supply of equipment for its oil and gas sectors.
So far the EU sanctions have had little effect on the regime of Syrian President Bashar Assad. Activist groups estimate nearly 7,500 people have died in 11 months of unrest.
As he left the meeting, French Foreign Minister Alain Juppe said he thought the imposition of new sanctions would be effective as part of a broader effort to put pressure on the Assad regime.
"It will not be enough, of course, but it is a new step," he said.
The foreign ministers had recognized the Syrian National Council, one of two main opposition groups, as one legitimate party to talk with, he added. But he acknowledged there were other elements opposed to Assad's rule and said it was important to push the opposition to become more organized.
Juppe said, too, that humanitarian access to those in need in Syria was "an absolute priority."
The names of the Syrian officials sanctioned Monday will be made public Tuesday in the EU's official journal. The new sanctions were adopted Monday morning by the foreign ministers of the 27 EU countries, meeting in Brussels, said Maja Kocijancic, an EU spokeswoman.
The officials are also expected to discuss Egypt's transition to democracy, and to urge a complete transfer of power to civilian rule as soon as possible.
In addition, they are expected to ease sanctions on the West African country of Ivory Coast, lifting visa bans on all but 15 people but keeping in place an arms embargo. The country erupted in turmoil last year when the incumbent president, Laurent Gbagbo, refused to leave power after losing an election to Alassane Ouattara.
Gbagbo has since been arrested and is in custody at the International Criminal Court in the Hague, Netherlands, where he faces charges including murder and rape.