If you exit back to the main menu, can you try creating a different profile and seeing if you can start a game?

Did you try verifying local files?

Are you shutting down all non-essential programs (especially anti-virus) before starting the game?

Try browsing to the '..\Documents\Larian Studios' folder and renaming the 'Divinity Original Sin' subfolder.
This folder contains the saved games, configuration files and a level cache folder. Deleting or renaming it will get the game to recreate it on startup; playing the game from a different Windows user account would effectively do the same thing.