Polylactic acid (PLA), poly-(L-lactied-co-ε-caprolactone-diOH (PCLA) and carboxylic-functionalized poly(arylene ether ketone) (PCA-PAEK) are the common used template polymers for preparing functional oxides through electrospinning technique. It has been found that the morphology of the oxide nanomaterials prepared by different polymer templates has great difference. This may be closely related to the thermal stability and thermal behavior of the polymers. However, there are few reports on this aspect. Therefore, in this paper, the thermal stability and thermal behavior of the electrospun PLA, PCLA, PCA-PAEK nanofibers were made comparison and analysis by TGA, DSC and SEM. The results showed that the morphology change temperature of PLA, PCLA and PCA-PAEK were 187℃, 127℃ and 300℃, respectively. This indicated that the thermal stability of the three polymers from high to low was PAEK, PLA and PCLA, successively. The research will provide a theoretical basis for the preparation of functional oxide nanomaterials with different morphologies.