The KTa 0.6 Nb 0.4 O 3 sols for chemical solution deposition of thin films were prepared from potassium acetate and transition metal ethoxides by the 2-methoxyethanol based route. The local environment of both transition metals after reflux times 1 h, 4 h, 24 h, and 48 h, whereby the crystallization behavior of the films was strongly affected, was monitored by extended X-ray absorption fine structure spectroscopy (EXAFS), at Ta L 3 and Nb K edges. The Ta species existed in the sols as monomers, remaining stable even with prolonged reflux time. TheTa-O-K correlations were confirmed in all cases. In contrast, the Nb-alkoxide formed dimers, with a gradual formation of oligomeric species with prolonged refluxing. The Nb-O-K correlations were present after all reflux times. The number of K neighbours around Nb increased upon refluxing, saturating at 24 h.