Cenospheres are the value-added components within coal combustion fly ashproduced by thermal power plant. With an aim to respond to the industrial expansion of cenospheres utilization, this work presents a study on recoveryprocess of hollow-sphere structured cenospheres from Class C high CaO fly ash,focusing on separation mechanism and efficiency, and (calcium, aluminium,silicon) compound composition relating to their surface reaction. Approaches toimproving the cenospheres separation efficiency have been investigated,combining with a characterization of physical and chemical properties, morphologies, and elemental composition of those collected cenospheres. Thiswork has made a systematic comparison of cenospheres separation efficiencyamong those obtained recovery percentages. Wall thickness-size-densityrelationship of the porous cenospheres has been established as a function of thewet separation parameters, demonstrating an insight regime into the intrinsicallyphysical nature of cenospheres in coal fly ash. The results have revealed that theoptimum ratio of fly ash to water is a considerable factor determining both qualityand quantity of cenospheres, herein found it a direct result from the wetseparation mechanism as basically depending upon the material-medium densitydifference. The recovery percent of cenospheres has appeared to relate, to someextent, to their chemical composition. The chemical reactions occurring on thecenospheres surface during the wet separation has been presumed to significantlycontribute their effect on the recovery percent. An overview of the up-scalingprocesses are also to be mentioned.