If you simply mean having one of the main menu items appear to the very right of the menu bar, try adding float:right to it in the HTML, for example:
Code:
<div id="ddtopmenubar" class="mattblackmenu">
<ul>
<li><a href="http://www.dynamicdrive.com">Home</a></li>
<li style="float:right"><a href="http://www.dynamicdrive.com/new.htm" rel="ddsubmenu1">DHTML</a></li>
<li><a href="http://www.dynamicdrive.com/style/" rel="ddsubmenu2">CSS</a></li>
<li><a href="http://www.dynamicdrive.com/forums/">Forums</a></li>
<li><a href="http://tools.dynamicdrive.com/" rel="ddsubmenu3">Web Tools</a></li>
</ul>
</div>
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