Besides primary carbides, so-called secondary carbides are usually observed in high-speed steel (HSS) microstructure, which precipitate from the oversaturated solid solution upon its cooling. Some of the secondary carbides precipitate from an oversaturated austenite at cooling during solidification or quenching, in both cases, in the form of the relatively big particles in the bulk of a matrix. Considerably finer secondary carbides precipitate in martensitic condition during tempering inducing secondary hardening in HSSs. In general, secondary carbides of both types have obvious effect on the fracture mode of HSSs. The precipitation of secondary carbides in HSSs in solidified and heat-treated conditions has been investigated. The microstructures of HSSs have been examined using light and electron microscopy (both scanning and transmission), X-ray diffraction analysis, and energy dispersive X-ray spectrometry. Results indicate that diffusion of both carbon and alloying elements plays an important role in the secondary carbide precipitation in HSSs.