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The paper was aimed at the PMMA/HNTs composite nanoifbers with well enhanced mechanical properties prepared by electrospinning technique for the first time. A series of characterizations were used to illustrate the structure and properties of the composite nanofibers by SEM, XRD, FTIR and DSC techniques. The effect of the PMMA/HNTs composite nanofibers in relationship to the mass percentage of HNTs was investigated. The results indicated that HNTs wrapped in polymer matrix were highly oriented and dispersed by the electrospinning technique, resulting in improved thermal stability of the polymer. Moreover, the mechanical properties of the PMMA/HNTs composite nanoifbers which were dependent on HNTs mass content were measured, and good enhanced mechanical properties were obtained.