Perovskite potassium tantalate niobate (KTN) powders and thin films were synthesized from a metal alkoxide solution. Homogeneous KTN coating solutions were prepared from KOC2H5, Ta(OC2H5)5, and Nb(OC2H5)5in absolute ethanol. The precursor crystallized to pyrochlore at ∼ 650°C, and then to perovskite at ∼ 750°C, depending upon Ta:Nb ratio. H2O vapor during calcination was found to play a prominent role in the direct and predominant crystallization of perovskite films with preferred orientation. Highly oriented KTN films of perovskite structure were successfully prepared on MgO (100) substrates at