Rapidly solidified particles of high-speed steel were classified into several granulometric fractions ranging from less than 25 μm up to more than 160 μm in diameter and studied by transmission and conversion electron Mössbauer spectrometry. The former was applied at 300, 77, and 5 K. Presence of magnetic and a non-magnetic crystallographic phase was observed. They were identified by X-ray diffraction as ferrite (bcc-Fe) and austenite (fcc-Fe), respectively. In addition, M 4 C 3 and M 2 C carbides were found. The magnetic phase diminishes in the bulk of the particles bigger than 63 μm (transmission Mössbauer spectroscopy) and/or 80 μm (X-ray diffraction). Its contribution is higher at the surface of the particles (conversion electron Mössbauer spectrometry). The origin of the non-magnetic phase is not changed even at 5 K. Reasonable agreement is achieved between Mössbauer and X-ray diffraction data as far as the fraction of Fe-containing phases is concerned.