Javier Solana said no Russian approval would be needed for the deployment, which would be made at Georgia's request.
Western countries have denounced Russia's August 26 decision to recognize Abkhazia and South Ossetia as independent states as "irresponsible."
They also criticized Moscow's response to Georgia's August 8 attack on South Ossetia as "disproportionate," and have said that Russia is failing to keep to the terms of the peace plan by keeping peacekeepers in buffer zones in Georgia.
Solana said around a hundred monitors would be deployed after approval from the European Union in the next few weeks.
He said 40 European observers had already been deployed to Georgia. He also pledged that the European Union would voice its political and economic support for the ex-Soviet republic at an emergency summit on Monday.
He said prospects for Russia-EU relations would be discussed further at the bloc's foreign ministerial meeting in Avignon, France, on September 5-6. The observer mission in Georgia and the deployment of peacekeepers will also be considered.
The EU official said he was "unaware" whether a decision would be made in Brussels later in the day to freeze talks with Russia on a new partnership and cooperation agreement. He also denied that the issue of sanctions against Russia was on the agenda of the coming meeting.
A number of member states, including Britain and Poland, have called for sanctions against Moscow, as well as the postponement of Russia-EU talks on a new partnership deal.
Britain has called on the EU to suspend talks on the partnership and cooperation agreement with Russia, an official from Prime Minister Gordon Brown's office told reporters on Monday.
Brown wrote on Sunday in the Observer newspaper that, "In the light of Russian actions, the EU should review - root and branch - our relationship with Russia."
Latest reports quoted Solana as saying he could soon visit Moscow and Tbilisi. He also said that he was sure that a Russia-EU summit would be held in November.
