The EU said it will also announce Tuesday additional financial and travel sanctions on several Iranian companies and "senior experts" linked to Tehran's nuclear program.
"The individuals will be banned from entering the EU and the entities will be banned from operating in the EU," an EU official, who wanted to remain anonymous, told Reuters after EU ministers met in Luxembourg. EU leaders agreed on the measures at talks in Brussels on Friday.
European officials did not give details of those added to the list but said they were officials and experts identified as having connections with Iran's nuclear and weapons programs.
No Iranian political leader was hit by the sanctions, because "we want to have a dialogue," a diplomat told the Agence France-Presse.
The 27-nation bloc is also studying sanctions against Iran's oil and gas sector, but such a step would probably take several months to implement, diplomats say.
In Tehran, independent analyst Saeed Laylaz told the Associated Press that freezing Bank Melli's assets would lead to the Iranian economy becoming more isolated and more dependent on Chinese products. He suggested President Mahmoud Ahmadinejad might stand to benefit.
Targeting Iran "drives inflation up," Laylaz said, "but it helps Ahmadinejad's government hide its failures behind the sanction."
The United States placed the bank on its blacklist last year, a measure that allows the freezing of any assets found in the United States.
During President Bush's farewell trip to Europe last week, Prime Minister Gordon Brown announced Britain would freeze the bank's assets and said Britain would work to persuade Europe to follow suit.
Last week, EU Foreign Policy Chief Javier Solana offered new incentives to Tehran but has not received a reply. Iran insists its nuclear program is peaceful but is defying a demand from the UN that it stop the enrichment of uranium.
In March, the United Nations Security Council approved a third round of sanctions against Iran over the issue.