<jats:p>Four analogs of the acetylenic alkaloid, histrionicotoxin (C<jats:sub>19</jats:sub>H<jats:sub>25</jats:sub>NO) and the allenic alkaloid, isodihydrohistrionicotoxin have been isolated from extracts of skins of the arrow poison frog, <jats:italic>Dendrobates histrionicus</jats:italic> and characterized as neodihydrohistrionicotoxin, tetrahydrohistrionicotoxin, isotetrahydrohistrionicotoxin and octahydrohistrionicotoxin. These spiropiperidine (8‐hydroxy‐1‐azaspiro[5.5]undecane) alkaloids differ only in the degree of unsaturation in the five carbon atoms (position 2) and four carbon atoms (position 7) side chains. A fifth compound, HTX‐D, corresponds in empirical formula to a tetrahydrohistrionicotoxin with a 7‐(<jats:italic>cis</jats:italic>‐1‐butenyl‐3‐ynyl) side chain, but the major mass spectral fragmentation with loss of C<jats:sub>2</jats:sub>H<jats:sub>5</jats:sub>O is not characteristic of the histrionicotoxins. Reduction of histrionicotoxin with hydrogen and <jats:italic>Lindlar</jats:italic> catalyst affords an isomeric dihydrohistrionicotoxin with the terminal acetylene of the five carbon atoms side chain reduced, tetrahydrohistrionicotoxin and hexahydrohistrionicotoxins, while reduction with hydrogen and palladium on charcoal affords dodecahydrohistrionicotoxin which is readily methylated to the tertiary amine by methyl iodide.