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.
If that fixes the problem (a new game can save/load), then copy your existing saves from the renamed folder to the newly created one. Each save is a folder in the '..\Documents\Larian Studios\Divinity Original Sin\PlayerProfiles\<ProfileName>\Savegames' folder.
