Nanograined (grain size 6-15 nm) ZnO films with various Fe content (between 0 and 40 at.%) were synthesized by the novel liquid ceramics method. The films with 0, 0.1, 5 and 10 at.% Fe contain only ZnO-based solid solution with wurtzite structure. The films with 20 at.% Fe contain mainly amorphous phase. The peaks of the second phase (ZnFe2O4 with cubic lattice) become visible in the X-ray diffraction spectra at 30 at.% Fe. Therefore, the overall solubility of Fe in nanograined ZnO films at 550 A degrees C is about 20 at.% Fe. The solubility limit in the bulk is about 1.5 at.% Fe. The recently published papers on the structure and magnetic behaviour of Fe-doped ZnO allowed us to obtain the dependence of Fe solubility in ZnO on the grain size. The overall Fe solubility drastically increases with the decreasing grain size. The quantitative estimation shows that, close to the bulk solubility limit, the thickness of a Fe-enriched layer in grain boundaries is that of several monolayers.