The Senegalese sponge Microscleroderma spirophora has been found to produce exclusively very unusual 3 beta-methoxysteroids in place of the common 3 beta-hydroxysteroids. Six different methoxysteroids (three of which are novel compounds) have been isolated and identified by spectroscopic means (MS, IR, 1H and 13C NMR), and their taxonomic significance discussed. A new method for the determination of the configuration at C-24 in saturated 24-ethyl side chains is also proposed.