Fe, Co and Si powders were exposed to mechanochemical activation by high-energy ball milling for 0, 2, 4, 8 and 12 h. The samples were subsequently characterized by Mössbauer spectroscopy, X-ray powder diffraction (XRPD), magnetic measurements and optical diffuse reflectance spectroscopy. The room temperature Mössbauer measurements were consistent with the occurrence of FeCo2Si and Fe0.5Co0.5Si crystalline phases. The low temperature Mössbauer spectra confirmed the absence of superparamagnetism up to 44 K in the milled system. XRPD patterns supported the phase sequence derived from Mössbauer spectroscopy. The coercive field was found to increase with the ball milling time (BMT). Zero-field-cooling-field-cooling (ZFC-FC) measurements performed at 200 Oe in the temperature range 5–300 K evidenced the transition to the skyrmion phase of the Fe0.5Co0.5Si material below the critical temperature of 44 K. The optical absorption in the UV–Vis–NIR region of the spectrum was found to increase with BMT.