The paper aims to investigate the effect of elements addition, its enthalpy of mixing, crystal structure and atomic size difference on the formation of solid solution phase during the synthesis of high entropy alloy (HEA) by mechanical alloying. For this CoCrFeNiX and CoCuFeNiX (where X = Ti, Zn, Si, Al), alloys were prepared by mechanical alloying. The phases formed during mechanical alloying were characterised by X-ray diffraction analysis, transmission electron microscopy and differential scanning calorimetry. Titanium and Aluminium addition facilitate solid solution formation during mechanical alloying. Formation of a BCC and FCC solid solution phase was observed for CoCrFeNiX and CoCuFeNiX system (where X = Ti, Al), respectively. Single solid solution phase was not observed for CoCrFeNiZn, CoCrFeNiSi, CoCuFeNiZn and CoCuFeNiSi HEA up to 20 hours of milling.
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