Two series of xHfO2 - (100-x) SiO2 (x=10, 20, 30 mol%) glass-ceramics planar waveguides doped with 0.3 mol% Er3+ ions were prepared by the sol-gel route. A thermal treatment at 1000°C was applied to the second series of samples to nucleate HfO2 crystals. The waveguides were analyzed by X-ray photoelectron spectroscopy to study the effect of the Hf concentration and of the annealing on the material structure. XPS shows that in the first series of samples a Hf concentration threshold exists. Above this threshold the material undergoes a spinodal decomposition with formation of HfO2 rich domains. In the second series of samples the presence of thermal treatment lowers the concentration threshold so that the phase separation occurs also at a Hf concentration of 10%mol. In the waveguides where spinodal decomposition in present, the emission spectra from the Er3+ ions reveal a sensible narrowing of the 4I13/2 → 4I15/2 line. This demonstrates the presence of a crystalline environment for the Er3+ ions since the inhomogeneous broadening due to the disordered glassy network is suppressed. These results may have important implications for the fabrication of photonic devices with increased efficiency.