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The interplay of mineralogical variation and mineral phase distribution within varying particle sizes on the dissolution behaviour of a low grade complex sulphide ore was investigated through bioleaching experiments and electrochemical technique. Investigations were carried out utilizing mineralogical data on the variations in mineral and phase distribution within particle sizes of＜53 μm, 53-75 μm, 75-106 μm and 106-150 μm in mixed mesophilic cultures of Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans and Leptospirillum ferrooxidans. Electrochemical behaviour was studied using particulate electrodes from the four varying particle sizes and from massive electrodes prepared from the two major sulphide mineral rich phases (sphalerite-rich and galena-rich) and a complex mineralogical phase of the bulk ore. Bioleaching studies reveal the highest recoveries at a particle size of 75 μm, while electrochemical investigations reveal the highest dissolution at particle size of 106 μm. Electrochemical results show that sphalerite rich phase has the highest dissolution rate while galena-rich complex phase has the least. SEM studies confirm the highest bacterial attack at the sphalerite-rich phase. The discrepancies between the dissolutions within particle sizes obtained from bioleaching experiments and electrochemical studies are consistent with and attributed both to the physical and mineralogical influences. Electrochemical behaviour is influenced and controlled by galvanic interaction resulting from mineralogical variation, while bioleaching behaviour is influenced by mineralogical variation as well as physical effect of particle size.