We present the structure and magnetic properties of the honeycomb anhydrate NaNi2BiO6-δ and its monolayer hydrate NaNi2BiO6-δ·1.7H2O, synthesized by deintercalation of the layered α-NaFeO2-type honeycomb compound Na3Ni2BiO6. The anhydrate adopts ABAB-type oxygen packing and a one-layer hexagonal unit cell, whereas the hydrate adopts an oxygen packing sequence based on a three-layer rhombohedral subcell. The metal-oxide layer separations are 5.7 Å in the anhydrate and 7.1 Å in the hydrate, making the hydrate a quasi 2-D honeycomb system. The compounds were characterized through single crystal diffraction, powder X-ray diffraction, thermogravimetric analysis, and elemental analysis. Temperature-dependent magnetic susceptibility measurements show both to have negative Weiss temperatures (-18.5 and -14.6 K, respectively) and similar magnetic moments (2.21 and 2.26 μB/Ni, respectively), though the field-dependent magnetization and heat capacity data suggest subtle differences in their magnetic behavior. The magnetic moments per Ni are relatively high, which we suggest is due to the presence of a mixture of Ni(2+) and Ni(3+) caused by oxygen vacancies.