Zinc borates are very important industrial materials with applications that include fire retardants and preservatives in wood. In this work, we report the preparation of three novel zinc borates: [Zn(NH3)3B4O5(OH)4]·H2O (ZB1), Zn3(H2B3O7)2·2NH3·4H2O (ZB2), and [Zn(NH3)4][B4O5(OH)4]·4H2O (ZB3). The solid phases were characterized by elemental analysis, X-ray diffraction, infrared and Raman spectroscopy, scanning electron microscopy and thermal analysis. The crystal structures of ZB1 (monoclinic, Cc, a = 12.1972(8), b = 7.8314(5), c = 12.1441(8) Å and β = 107.404(5)°) and ZB3 (orthorhombic, Pbca, a = 15.0796(9), b = 11.8853(5) and c = 16.7606(8) Å) were determined. They are novel neutral Zn-polyborate complexes [Zn(NH3)3B4O5(OH)4] hydrate and [Zn(NH3)4][B4O5(OH)4] tetrahydrate salt, respectively. The complete assignment of infrared and Raman spectra was performed theoretically using DFT calculations. For ZB2 (obtained as a polycrystalline phase), powder X-ray diffraction confirmed a single phase and allowed the determination of the unit cell parameters and lattice type (rhombohedral, a = 36.78076 (6), c = 12.20052 (3) Å) with an expected formula Zn3(H2B3O7)2·2NH3·4H2O suggesting that this compound is a complex triborate. Furthermore, a low-cost scalable synthetic procedure for ZB1 starting from zinc oxide and boric acid in ammonia solution with a high yield is also reported.