They are kind of similar, in that they both promote lots of fresh foods, both prefer seafood over beef, etc. But the specific focus of each plan is a little different.
Volumetrics looks more at the water content of foods, and the energy density. You eat more foods that give lots of volume for few calories. Like grapes, for example. It teaches you how to walk away from the table feeling full on fewer calories. We wrote about Volumetrics here -
http://www.3fatchicks.com/diets/volumetrics.php
The Mediterranean diet doesn't really consider these things in the scheme of things, but focuses on more natural (less processed) foods such as vegeteables, whole grains, seafood, and good fats.
The biggest difference that I can think of at the moment, and in my opinion, would be the amount of fat with each diet. Volumetrics is a lower fat diet, while the Med diet would usually be a moderate fat (though good fat) diet. However, it would be easy to combine the two.