Did you try verifying local files? In the Steam library, right click on Divinity Original Sin and select Properties, switch to the Local Files tab and then click on the 'Verify Integrity of Game Cache...' button.
Try browsing to the '..\Documents\Larian Studios' folder and deleting the 'Divinity Original Sin' subfolder.
This folder contains configuration files and a level cache folder, and would contain saved games if you were able to get that far. 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.
Crash on startup [Solved]Please email supportdos@larian.com, with a description of the problem and the report.zip file generated by the
D:OS support tool (for the PC version). The report will contain system and game information, any crash dumps, and (if they existed) your saved games.