1. Arapaima gigas bile salts were hydrolysed by alkali or cleaved with dioxan–trichloroacetic acid to give cholic acid, arapaimic acid, arapaimol-A and arapaimol-B. 2. I.r., n.m.r. and mass spectroscopy and [α]D measurements indicated that arapaimic acid and arapaimol-A and -B are respectively 2α,3α,7α,12α-tetrahydroxy−5β,25∈-cholestan-26-oic acid, 5β,25R-cholestane-2β,3α,7α,12α,26-pentol and 5β-cholestane-2β,3α,7α,12α,26,27-hexol. 3. Partial synthesis of 2β,3α,7α,12α-tetrahydroxy−5α- and −5β-cholan-24-oic acid and their spectral examination fully confirmed these conclusions. 4. A. gigas bile salts show primitive features in that they comprise alcohol sulphates and a C27 acid; they are also specialized in showing 2β-hydroxylation.