In this study, adsorption of three different heavy metals i.e. cadmium (Cd (II)), copper (Cu (II)) and nickel (Ni (II)) was carried out in single and multi-contaminated system using coal-fired fly ash (CFFA). Initially, for the single contaminated system, various physical process parameters were selected for optimization by deploying Box–Behnken design of experiments. Further, the evaluation of CFFA for removal of heavy metals in a multi-component system from aqueous solution was performed by employing Plackett-Burman design of experiments with all the three heavy metals at two different levels by varying their initial concentration (10–50 mg L −1). In both the aforementioned cases, CFFA showed its great potential for heavy metal removal, i.e. single and multi-component system and followed the order: Cu (II) > Ni (II) > Cd (II). Further, FTIR study confirmed the involvement of amide, aldehyde, alkoxy, alkanes, and alkene groups for heavy metal adsorption by CFFA.