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This guide will explain the basics of paint.net and using it to save League textures.
The links below will take you to the download page. Click the download button in the top right and download. When downloaded, extract the .zip file and run the installer.
paint.net comes with DDS support out of the box.
Go to File/Save As. From the dropdown menu pick DirectDrawSurface (DDS) (*.dds) and save click save.
A new menu will open. In the first dropdown menu you will need to select Bc3 (DXT5).
Don't edit other settings and click OK.