Grotea ambarosa sp. nov. is described, illustrated and compared to currently described species of the genus. The new species is characterized mainly by having the mesosoma 2.9× as long as high; genal projection distinct and apically subquadrate; pleural carina distinct only anteriorly to anterior transverse carina; mesosoma almost entirely amber-orange and legs with complex dark brown and white marks. This is the first record of any labenine species for the Greater Antilles; the few distribution records elsewhere in the Caribbean Islands are reviewed and discussed in the context of the biogeography of Labeninae.