We reviewed specific chemical exposures and exposure assessment methods relating to published and unpublished epidemiological studies in the alumina and primary aluminium industry. Our focus was to review limitations in the current literature and make recommendations for future research. Although some of the exposures in the smelting of aluminium have been well characterised, particularly in potrooms, little has been published regarding the exposures in bauxite mining and alumina refining. Past epidemiological studies in the industry have concentrated on the smelting of aluminium, with many limitations in the methodology used in their exposure assessment. We found that in aluminium smelting, exposures to fluorides, coal tar pitch volatiles (CTPV) and sulfur dioxide (SO2) have tended to decrease in recent years, but insufficient information exists for the other known exposures. Although excess cancers have been found among workers in the smelting of aluminium, the exposure assessment methods in future studies need to be improved to better characterise possible causative agents. The small number of cohort studies has been a factor in the failure to identify clear exposure-response relationships for respiratory diseases. A dose-response relationship has been recently described for fluoride exposure and bronchial hyper-responsiveness, but whether fluorides are the causative agent, co-agent or simply markers for the causative agent(s) for potroom asthma, remains to be determined. Published epidemiological studies and quantitative exposure data for bauxite mining and alumina refining are virtually non-existent. Determination of possible exposure-response relationships for this part of the industry through improved exposure assessment methods should be the focus of future studies.