Nope, you can't block while waiting for a Web request, nor would you want to (your app will appear to have crashed).
You can split your app in to 2 scenes, 1 would be the loading scene that does the WWW request and then loads your main scene. Any data that the WWW gets can be stored on your gameObject by marking it as "don't destroy on load".
http://docs.unity3d.com/Documentation/ScriptReference/Object.DontDestroyOnLoad.html
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