When you double-click on one of the rows on the main dialog, FreeFileSync opens the operating system's file browser by default. On Windows it calls explorer /select, "%item_path%", on Linux xdg-open "%item_folder%" and on OS X open -R "%item_path%".
You can customize this behavior and integrate other external applications into FreeFileSync: Navigate to Menu → Tools → Global settings: Customize context menu and add or replace a command. The first entry is executed when double-clicking a row on main grid or pressing ENTER while all other entries can be accessed via the context menu shown after a right mouse click. The following macros can be used: