The decision was made out of concern for the political situation in the country and the treatment of opposition leader Yulia Tymoshenko, Androulla Vassiliou said.
Vassiliou joins Commission president Jose Manuel Barroso and justice commissioner Viviane Reding, who had earlier pledged not to attend games in Ukraine.
"We have seen a lot in the news in the past few days regarding the possible attendance of the competition by politicians in response to concerns over the political situation in Ukraine.
I share these concerns, which is why I have decided, in my capacity as the European Commissioner responsible for sport, that it would not be appropriate under the current circumstances for me to attend any matches taking place in Ukraine. This view is shared by the President and the other members of the European Commission.
In this respect, I align myself fully to the statement made last week by the High Representative of the European Union for Foreign Affairs and Security Policy and Vice President of the Commission, on the situation of Yulia Tymoshenko," Vassiliou said in a statement, ForUm learned from the press office of the Commissioner.
At the same time the officials hope for the tournament's success, despite their declarations on boycotting.
"Like millions of sport fans, I am looking forward to this summer's EURO 2012 football championships with great anticipation. The tournament will provide a stage for some of the world's best players and I'm sure we will see some thrilling matches and, hopefully, plenty of goals.
Despite the situation, I think it is important to preserve the real essence of sport and the sporting success of EURO 2012.
Indeed, I very much hope that this football tournament will be a true success and that I will be able to attend one of the matches taking place in Poland," the same statement says.
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