Solana is to meet with President Mikheil Saakashvili and other Georgian officials and visit a South Ossetian refugee camp in the city of Gori.
One hundred and forty EU military observers from 22 countries will replace the Russian peacekeepers in the buffer zone between Georgia and South Ossetia. The Russian forces will withdraw by October 10.
A senior EU official said earlier that more than 300 European Union staff - civilian monitors and support staff - were on the ground, and had begun deploying to field offices in western and central Georgia.
Moscow launched a five-day operation to "force Georgia to accept peace" after Tbilisi attacked South Ossetia on August 8 in an attempt to regain control over the republic, which split from Georgia in the early 1990s. A number of Russian peacekeepers and a reported 1,600 South Ossetian residents lost their lives during the conflict.
Russia's response to the Georgian attack was called disproportionate by a number of Western powers. On August 26, Russia drew further criticism when it recognized South Ossetia and Abkhazia, another breakaway Georgian republic, as independent states. So far, only Nicaragua has followed suit.
