Three dimensional, highly porous, ZrO2 scaffolds coated by glass–ceramic derived from 45S5 bioglass were fabricated. The surface reactivity of 45S5 in aqueous solution was investigated as a function of the immersion time. The influence of the solid loading on the rheological behavior of 45S5 aqueous slips with ammonium polyacrylate (NH4PA) was studied; besides the effect of poly(vinyl)alcohol (PVA) on the relative viscosity was determined. The structure and microstructure of uncoated and coated ZrO2 scaffolds were characterized. The high ionic exchange capability of 45S5 was demonstrated by the pH rise, the significant weight loss and the amorphous calcium phosphate nucleation, upon its immersion in aqueous solution. The addition of PVA did not affect the dispersion properties of the 45S5 powder, which were basically controlled by its negative surface charge. 30wt% 45S5 slips with 4wt% PVA exhibited a yield stress and an adequate viscosity in the low shear rate range, to produce a bioglass coating into the ZrO2 scaffold. The glass-ceramic coating was distributed along the strut surfaces, forming a thin film without altering the porosity and the strut thickness of the original ZrO2 scaffold structure.