For example, you can add your gravatar as follow:
ul > li.gravatar > a,
ul > li.gravatar > a:hover{
display:block;
padding-left:36px !important;
line-height:36px;
background-image:url(http://www.gravatar.com/avatar/9612f6e40110aaafcff8ab3cec54dc6e?s=32)!important;
background-position:left center !important;
background-repeat:no-repeat !important;
}
Then go to the Appearance\Menus, select your custom menu item and add “gravatar” class (with no quotes) to it in the CSS Classes text input field. If you do not see it, just click on the Screen Options link at the upper right corner of the window and check CSS Classes checkbox.
The menu item will look like at the example: http://2010.test.thethefly.com/