Two deep ultraviolet (DUV) hydroxylated-alkali-metal borates, NaRbB10O14(OH)4 (I) and Na3CsB10O16(OH)2 (II), have been successfully synthesized by a high-temperature solution and solvothermal method. Both of them feature [B5Om(OH)n] units, which form chains for (I) and bilayers with nine-membered boron rings for (II). It is worth noting that both compounds exhibit very wide theoretical band gaps of 7.33 and 6.55 eV for (I) and (II), respectively, which denotes that they should have desirable DUV transmittance ability. Moreover, the title compounds have moderate birefringence owing to the π-conjugated [BO3], [BO2(OH)] groups, corresponding to 0.070 for (I) and 0.054 for (II) at 1064 nm. The structure characteristics and optical properties were also investigated and discussed. The results make it beneficial for exploring novel DUV hydroxylated borate optical crystals.