Re: Please help. A serious error has occurred while loading Sunset Valley. New Game.
Even if you haven't played on this computer yet, you could still have some issue in your new TS3 folder in Documents. Since you have no content yet, why not just trash the folder and try again with a new one? And just checking, but are you trying to launch the game while any of its folders are open? If so, restart your computer and make sure all windows are closed before attempting to load the game.
You could also try disabling your antivirus software's realtime scanning. Some programs have been known to interfere with the launching of TS3.
It would be useful to know the specs of your computer as well, so that you can get more specific advice.