From Mac Rumors: New iTMS Localizations Tuesday? [Updated]:

Think Secret says the the iTunes Music Store should have an October 26th rollout into several European countries, as well as Australia and other venues. Various MacRumors readers report that the iTMS is currently unavailable for browsing from their countries today, suggesting the localizations for them may be just around the corner. Those reports include Switzerland, Austria, Ireland, and Canada, with users being greeted with a new message stating “iTMS is not available in your country yet.”

[Update] – Additional countries as reported by MacRumors.com readers

Spain

Norway

Finland

Netherlands

Sweden

Japan

Italy

Belgium

Poland

New Zealand

Denmark

Mexico

Iceland

If this is indeed the case, Luxembourg is once again not in the game I have the message “iTMS is not available in your country yet.” but have no problems surfing the four existing stores after I click on the OK button. No change here.

As with the Apple Store, the customers living in Luxembourg are not able to buy directly from Apple. The iTMS will not be accessible from Luxembourg either I suppose… One should consider a bank account in a neighbour country…