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There are eight genera of Polygalaceae in Ecuador: Acanthocladus (2 spp.), Badiera (1 sp.), Bredemeyera (1 sp.), Monnina (39 spp.), Moutabea (1 sp.), Polygala (6 spp.), Pteromonnina (4 spp.), and Securidaca (10 spp.). It is also expected that one species of Diclidanthera occurs in the country. Ten new species are described: Acanthocladus guayaquilensis B. Eriksen & B. Ståhl, Monnina alinae B. Eriksen, M. carmelensis B. Eriksen, M. neurophylla B. Eriksen, M. pichinchensis B. Eriksen, M. pycnophylla B. Eriksen, M. reticulata B. Eriksen, M. splendens B. Eriksen, Polygula vilcabambae B. Eriksen & B. Ståhl, and Securidaca fragilis B. Ståhl & B. Eriksen. Six new combinations are made: Acanthocladus scleroxylon (Ducke) B. Eriksen & B. Ståhl, Badiera caracasana (Kunth) C. Persson, Monnina hirta (Bonpl.) B. Eriksen, M. hirta var. cuspidata (Benth.) B. Eriksen. M. ligustrina (Bonpl.) B. Eriksen, and M. phillyreoides (Bonpl.) B. Eriksen, and one new name is introduced. Monnina bonplandiana B. Eriksen. Descriptions, keys, and specimen citations are given for all taxa and representative species are illustrated. The chromosome number 2n = 20 (or n = 10) is reported for 11 species of Monnina. whereas one species (M. crassifolia) was found to have 2n = 40 and another one (M. bonplandiana) 2n = 30.