The structures of polymastiamides B-F (2-6), five new steroid/amino acid conjugates isolated from the Norwegian marine sponge Polymastia boletiformis, have been solved by spectroscopic analysis of their desulfated methyl esters 8-12, respectively. Polymastiamides were found to undergo double-bond migration during treatment with MeOH/HCl to give the Δ14,15 artifacts 13 to 16. A C-ring benzenoid artifact 17 was also obtained from the methylation reaction.