Last month the Apache Infrastructure Team fell victim to a common web application attack. Rather than keep the information secret, they were kind enough to explain how the attack occurred. The initial attack leveraged cross-site scripting to steal users' session IDs. This is something that could have been prevented if the web app's session cookie had been marked with the HttpOnly attribute. When a web app sets a cookie, the presence of HttpOnly instructs browsers to disallow client-side script from accessing the cookie.
You will sometimes hear or read that HttpOnly helps prevent XSS attacks. That is not quite true. It helps prevent session hijacking. Specifically, it helps guard against one attack vector, namely where session cookies are stolen via XSS. HttpOnly can be used for any sensitive cookie that you don't want falling into the hands of fraudsters. (I should use "fraudster" more often - it is a fun word)
There is one caveat to using HttpOnly. It might break your application if it was written in such a way that the functionality depends on JavaScript having access to the cookie. That is fairly uncommon however.