While it is believed that proteins may protect enamel from demineralisation, recent work has indicated that such material may also hinder remineralisation. For example, albumin will inhibit apatite crystal growth in vitro and is present in carious enamel in vivo. However, it is not clear whether (1) the distribution of proteins within lesions is restricted to specific lesion zones or (2) the origin of such proteins is endogenous (i.e. as a remnant of the developmental process) or exogenous, originating in the saliva or gingival crevicular fluid. The present study used a combination of immunohistochemistry and microradiography to determine the distribution of two proteins, serum albumin and salivary amylase, within natural white–spot carious lesions in relation to specific levels of demineralisation. The results indicated that albumin is found primarily in a region of between 10 and 20% demineralisation (an area of transition between the ‘dark’ zone and lesion ‘body’), with smaller quantities occurring in the region between 0 and 10% demineralisation and trace amounts in the zone indistinguishable from sound enamel by microradiography. A similar distribution was found for amylase in that the heaviest labelling was within the 10–20% demineralisation zone, although little if any was present in the 0–10% zone. The presence of these molecules in a region of the lesion where some potential for reprecipitation may exist will have important implications with respect to lesion progression.