Er 3+ -doped silica waveguides, co-doped with aluminium, titanium, and hafnium oxides, were prepared using the sol–gel method and dip-coating processing. Here, we present a characterisation of the local environment around Er 3+ ions, as determined from the Er L 3 -edge extended X-ray absorption fine structure (EXAFS) measurements performed at ESRF (France). The first coordination shell is composed of 5–6 oxygen atoms at distances 2.32–2.35 Å , slightly varying as a function of the modifier oxide. Er 3+ nearest neighbors distance does not show a significant compositional dependence. On the contrary, outer shells analysis shows significant differences: Al 2 O 3 doping (less than 2% mol) induces an ordering around Er and increases the distance of the second shell, probably due to the substitution of Si by Al atoms; for TiO 2 doping (7–15% mol), it is most probable that the second shell is composed from Si atoms as the case of pure SiO 2 ; for HfO 2 doping (from 10 to 50 mol%) there is a very clear evidence of Er–Hf coordination already at the lowest Hf content, but still in amorphous environment.