Phoxocephalopsids are fossorial amphipods endemic to the Southern Hemisphere and currently encompass five genera and 15 species, including the four new species herein described. Previous records of the family along the Brazilian coast are limited to Phoxocephalopsis zimmeri Schellenberg, 1931. Based on material from the Crustacean Collection of Museu Nacional/UFRJ four new species of Phoxocephalopsidae areherein described: Phoxocephalopsis ruffoi sp. nov. from Rio de Janeiro, São Paulo, Paraná and Rio Grande do Sul (23o-30oS); Puelche irenae sp. nov. from Espírito Santo and Rio de Janeiro (19o-23oS); Puelche longidactylus sp. nov. from Bahia, Espírito Santo and Rio de Janeiro (12o-23oS) and Puelche mourae sp. nov. found only at Rio de Janeiro. High diversity was recorded from the Campos Basin region, which extends from the north of Rio de Janeiro to south of Espírito Santo (21o-23oS), with the presence of all four phoxocephalid species. A key to Phoxocephalopsidae species from Brazil, including P. orensanzi Barnard and Clark, 1982 is provided.