parentElement is new to Firefox 9 and to DOM4, but it has been present in all other major browsers for ages.
In most cases, it is the same as parentNode. The only difference comes when a node's parentNode is not an element. If so, parentElement is null.
As an example:
document.body.parentNode; // the <html> element
document.body.parentElement; // the <html> element
document.documentElement.parentNode; // the document node
document.documentElement.parentElement; // null
(document.documentElement.parentNode === document); // true
(document.documentElement.parentElement === document); // false
Since the <html> element (document.documentElement) doesn't have a parent that is an element, parentElement is null. (There are other, more unlikely, cases where parentElement could be null, but you'll probably never come across them.)
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