Nanoscaled Ca1鈥?i>xYxF2+x (x = 0...0.40) was prepared on the new fluorolytic sol鈥揼el route using organic precursors and anhydrous HF. These nonstoichiometric fluorite-type phases were investigated using 19F MAS and 19F鈥?sup>89Y CP MAS NMR. Excess fluoride ions occur as point defects for x 鈮?0.01. For x > 0.01 excess fluoride ions start clustering. The 19F spectra of these phases can be fully explained by assuming a distribution of Ca2+ and Y3+ around fluoride ions. Y3+ is distributed within the crystal lattice of CaF2, with higher concentrations near fluoride clusters. Two different coordination polyhedra for Y3+ are observed. The correlation between 19F and 89Y signals was established.