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As the most fundamental unit of photonic integration, optical waveguides offer the possibility of developing efficient and practical photonic chips by facilitating the on‐chip integration of devices with different functions. Femtosecond direct laser writing (FsDLW), as a burgeoning 3D microfabrication technology, can realize the rapid formation of arbitrary optical waveguides without any mask inside versatile materials, such as crystalline dielectric crystals, glasses, polymers, and photoresists. This significant material‐independence allows FsDLW to combine different materials and manufacturing processes to implement a cross‐platform solution. This review first describes the different optical loss types and suitable measurement methods for different applicable scenes, then summarizes the two fabrication mechanisms and points out the general direction for adjusting the waveguide properties by fabrication processes. Finally, the application fields and development prospects of different materials are discussed by overviewing the characteristics of different materials and the material selection preferences of different devices. With a panoramic view of the development, it is concluded with insights and perspectives of the future development of optical waveguides and processing technology via FsDLW. [ABSTRACT FROM AUTHOR]