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How the role of dopamine differs according to the evolution of eusociality and how it is required in the flexible society of Polistes paper wasps need further clarification. In the present study, we compared the storage and usage of dopamine-related substances in brains between the castes of paper wasps. The head widths, lipid stores in the abdomen, and levels of biogenic amines in the brains were measured in newly emerged females before male emergence (workers) and after male emergence (gynes) in four Polistes species. The head widths and the lipid stores were significantly larger in gynes than workers in P. snelleni, P. rothneyi, and P. jokahamae, whereas they did not differ between castes in P. chinensis. The levels of dopamine precursors in the brains were significantly higher in gynes than workers in P. snelleni, P. chinensis, and P. rothneyi, whereas those of dopamine and its metabolites did not differ between castes in these species. In P. jokahamae, the levels of dopamine precursors and dopamine in the brains did not differ between castes, but those of a dopamine metabolite were significantly higher in gynes than workers. Thus, the caste differences in the levels of dopamine-related substances did not always match body sizes and nutritional reserves. Foundresses in P. rothneyi had significantly lower levels of dopamine precursors and higher levels of dopamine and its metabolite than newly emerged gynes. These results suggested that in several Polistes species, dopamine precursors were stored in the brain without dopamine biosynthesis at emergence, and then converted into dopamine in foundresses during colony founding. These neuroendocrinal states in Polistes species largely differed from those in eusocial bees.