(from http://doc.tikiwiki.org/tiki-index.php?page=Styles and Themes)
Tiki themes control both the layout or structure of a site and its overall look. You can alter the position of elements on your Web pages (adding/subtracting components) and you can modify stylistic elements like color and font. Thus, by creating or modifying a theme, you can define:
First, you'll need to create the basic layout of your new theme.
At this point, your new theme has been created! If you go to User Preferences and check the drop-down menu for Theme, you'll find your theme listed (e.g., screensite). But, without changing the TPL files, your new theme will look just the same as the pre-existing theme you based it on.
See next: Template Overview
CSS Overview
Under Admin > Login you can activate "Reg users can change theme".
Once activated users can change their theme in their Preferences page under My Tiki menu.
Under Modules you can also activate the switch_theme module which makes it super easy for users to change themes.
ThemeControlDoc on Tikiwiki.org is all about how to assign Themes to
If you enable the theme control center you will see a link to Theme Control in the Admin section of the application menu.