Amorphous ribbons of different thicknesses of Co_64.5Fe_3.5Si₁₆B₁₄Ni₂ alloy were synthesized using the melt spinning technique by varying wheel speed. The effect of cooling rate on the ribbon thickness and their soft magnetic properties have been studied. The amorphous structure has been characterized in terms of structural free volume and medium range order(MRO) by positron annihilation spectroscopy and fluctuation electron micros copy techniques. Positron life time spectra of amorphous samples showed two life time components. The first component was found to be correlated with MRO where as, the second life time component was found to be associated with nanovoid type of defects, and the second component was strongly dependent on processing conditions. It could be established that the coercivity of the amorphous samples produced by the rapid solidification technique mainly depends on the defects formed during processing rather than change induced in MRO.