To evaluate bacterial cellular polyamine distributions as a chemotaxonomic marker for classification and as a growth factor for extremophilic environments, acid-extracted polyamines from new available members including various extremophiles belonging to the emended phylum Proteobacteria including the classes, Alphaproteobacteria (164 strains), Betaproteobacteria (35), Hydrogenophilalia (3), Gammaproteobacteria (113), Acidithiobacillia (11) and Zetaproteobacteria (2), and the newly validated phyla Epsilonbacteraeota (22), Bdellovibrionota (2) and Myxococcota (1) separated from the former phylum Proteobacteria, were analyzed by HPLC and HPGC-MS. Distribution of homospermidine, spermidine and aminopropylcadaverine were found within Alphaproteobacteria. 2-Hydroxyputrescine and 2-hydroxyspermidine were found within Betaproteobacteria and Hydrogenophilalia. Occurrence of 1,3-diaminopropane and norspermidine was specific to certain members of Gammaproteobacteria. Only spermidine was detected as a major polyamine in Acidithiobacillia and Zetaproteobacteria. Spermidine was a major polyamine in Epsilonbacteraeota. Spermidine-dominant or homospermidine-dominant species were found within Bdellovibrionota and Myxococcota. Thermophilic species have a high level of spermine in the four phyla.No clear polyamine profile patterns were observed in acidophiles, alkaliphiles, psychrophiles and halophiles of the four phyla.