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This evening I setup 6.5, everything was relatively straight forward and I followed the same steps I used for 6.2. I always setup from the zip of the site and database, manually connecting everything up. The only time  I got stuck was when I tried to start the site for the first time and I received this error: I am setting this up on Vista (I can hear the screams of horror now), so you might not get this message. The solution to this problem is quite simple, it is caused by a conflict between the settings in the Web.Config of Sitecore 6.5 and the machines default config. To correct open the file C:\Windows\System32\inetsrv\config\applicationHost.config and search for the entry:
Update the overrideModeDefault attribute to Allow, save the file, reload the site and everything should work! When updating the default settings for your machine consider the other applications on your computer and any security implications.