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The Dolcevita theme is a beatiful CSS only theme that leverages Drupal default HTML markup. It supports color module and layout and style options that you can control through Drupal's UI.
To learn how to build your own custom theme and override Drupal's default code, see the Theming Guide: http://drupal.org/theme-guide
See the sites/all/themes/README.txt for more information on where to place your custom themes to ensure easy maintenance and upgrades.