The rapid development of the chemistry of fluorooxoborates is associated with their important role as valuable optical materials. In this work, we report the first two silver representatives of the family, Ag2B5O8F (1) and Ag3B5O8F2 (2). Both structures are based on pentaborate groups with different degrees of “fluorination”: 1 contains interpenetrating frameworks composed of [B5O10F] fundamental building units, while 2 consists of layers of [B5O10F2].