<p>Say I have a list as follows:</p>

<ul>
<li>item1</li>
<li>item2</li>
<li>item3</li>
</ul>

<p>Is there a CSS selector that will allow me to directly select the last item of a list? In this case item 3.</p>

<p>Cheers!</p>

Not that i'm aware of.  The traditional solution is to tag the first & last items with class="first" & class="last" so you can identify them.
The CSS psudo-class
first-child
will get you the first item but not all browsers support it. CSS3 will have
last-child too
(this is currently supported by Firefox, Safari but not IE 6/7/beta 8)