A review of the native species of Nymphaeaceae from Brazil is presented, in which two genera (Nymphaea and Victoria) and 23 species, are recognized. Of these, 16 have been previously described: Nymphaea amazonum, N. belophylla, N. conardii, N. gardneriana, N. glandulifera, N. jamesoniana, N. lasiophylla, N. lingulata, N. oxypetala, N. potamophila, N. prolifera, N. pulchella, N. rudgeana, N. tenerinervia, N. vanildae and Victoria amazonica; five are described as new species: N. caatingae, N. francae, N. harleyi, N. paganuccii and N. rapinii; and N. amazonum subsp. pedersenii was elevated to the species rank, as N. pedersenii. Lectotypes are designated to Nymphaea alboviridis, N. amazonum, N. fenzliana, N. lasiophylla, N. nervosa, N. tenerinervea, Victoria cruziana and V. regia, and a neotype is designaed to Victoria amazonica. The paper includes detailed descriptions, illustrations of all the species, as well as notes on their reproductive biology and taxonomy, providing the first complete account of the family for Brazil since that by Caspary in Flora Brasiliensis, in 1878.