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Zirconate fibrous membranes show promising applications in high thermal insulating areas for the high melting point, low thermal conductivity and good phase stability. To satisfy the high-temperature mechanical demands, the microstructure of zirconate fibers needs further modification to accommodate high-temperature stability. In consideration of the slow ion diffusion rate and enhanced stability of solid solution, Ca x Sr 1- x ZrO 3 fibrous membranes were electrospun with molar ratio of Ca/Sr varied from 0.9 to 0.5 for the present work. The effects of strontium precursor on the pyrolysis process, phase formation and microstructure evolution were fully characterized. Modified microstructures with smaller grain size and narrow particle size distribution were achieved. Furthermore, the NIR reflectivity, thermal conductivity, and high-temperature stability were also presented. The special expansion character of fibrous membrane at high temperature would make it promising candidate to compensate the shrinkage of other oxide fibrous membrane. [ABSTRACT FROM AUTHOR]