Free-standing La₂Zr₂O₇ coatings were obtained by plasma spraying, using an amorphous La-O-Zr precursor as the feedstock. The La-O-Zr precursor powder was prepared by coprecipitation. During thermal spraying, the formation of coatings can be regarded as a joint process of melting-solidification, thermal decomposition, and crystallization. The time required for crystal growth was significantly shortened during spraying. Consequently, the average grain size of coatings was approximately 200 nm, with a narrow distribution (100-500 nm). Coatings prepared by this method show better thermophysical properties than those prepared with crystalline La₂Zr₂O₇ powder as the feedstock. The thermal conductivity of the as-sprayed coating was approximately 0.36-0.47 W/m K and the average coefficient of thermal expansion (CTE) is 11.1 × 10⁻⁶/K.