As a result of titanium and zirconium alcoholates hydrolysis in the presence of dissolved Fe(acac)(3), amorphous iron-containing gels have been synthesized. Their heat treatment has led to polycrystalline double oxides FexZr1-0.75xO2-delta(C) and FexTi1-0.75xO2-delta (T) formation. It has been shown that oxides (C) and (T) are likely to be solid solutions with 0.01 < x < 0.17 and 0.01 < x < 0.14, respectively. On the basis of X-ray diffraction and extended X-ray absorption fine structure data, iron-zirconium and iron-titanium crystallite models for gels and oxides have been proposed. It has been found that the crystallization process does not lead to a significant change in interatomic distances typical for local structures detected in gels.