Calcium is purported to prevent colorectal cancer by forming insoluble complexes with bile acids and long-chain fatty acids in the large bowel. Therefore, a method for analysing calcium-lipid complexes in faeces has been developed to investigate this. The calcium soaps of a long-chain fatty acid (calcium palmitate) and bile acids (calcium deoxycholate, chenodeoxycholate, cholate and lithocholate) were obtained by organic synthesis. Studies with the authentic soaps reveal that they exist in an empirical ratio of calcium-to-lipid of 1:2. On addition to lipidfree faeces, approximately 30% of calcium palmitate could be recovered and quantified in the authentic state by extraction with 72% ethanol and overnight precipitation at 0° C. In contrast, the calcium soaps of the bile acids could not be recovered in the authentic state but were quantified entirely as the free acids. The method was applied to the analyses of calcium-lipid complexes in the faeces of adenoma patients partaking in a placebo-controlled calcium-intervention study. The results show that human faeces contain appreciable amounts of calcium long-chain fatty acid soaps predominantly in the form of calcium palmitate and stearate. The faecal concentration of long-chain fatty acid soaps was increased significantly (P = 0.005) during calcium intervention but this did not have a statistically significant effect on the excretion of free long-chain fatty acids (P = 0.4). Calcium long-chain fatty acid soap formation was found by multiple regression to be equally dependent on stool long-chain fatty acid and calcium concentration. Calcium soaps of the bile acids were not detected by this method. Studies with EDTA revealed that the ability of this divalent cation chelator to solubilize bile acids is independent of an association with calcium because free bile acids and bile acid soaps were solubilized to a similar extent. The solubilization of faecal bile acids was found to be significantly dependent on both total and primary bile acid concentration. The method needs further development before faecal bile acid soaps (if they exist) can be adequately evaluated.