The structure of Zr atomic environment in a CaO-ZrO2-SiO2 glass-ceramic has beenstudied combining x-ray absorption spectroscopy (XAS), X-ray diffraction (XRD) andanomalous-XRD (a-XRD) techniques as a function of thermal treatments. The analysisof XRD patterns demonstrates that the devitrification process, as a function ofthermal treatment, proceeds through the partial segregation of Zr-depleted phases(Wollastonite-like) and Zr-rich phases (Zr-oxides). The XAS and a-XRD measurementsat the Zr K edge have been exploited to get a closer insight on the atomicstructure around Zr ions. In the as quenched glass the Zr is 6-fold coordinated to Oxygenatoms in an amorphous environment rich of Ca and Si. Thermal treatment firstly(T=1000 - 1050 oC) determines the partial segregation of Zr in form of oxide whichcrystalline structure is that of tetragonal Zirconia (t-ZrO2). Raising the temperature(T=1100 oC) provokes the formation of ZrO2 crystallites in the monoclinic crystallographicphase (Baddeleyite: m-ZrO2). The analysis of XAS data demonstrates that aconsiderable amount of Zr still remains in an amorphous Calcium-Silicate phase
