In this study, we report the structure and shape of new polymeric nanofibers entrapped with QDs, which were prepared by electrospinning a homogenous mixture of polymers and QDs. Uniformly distributed QDs within the polymer matrix seem to induce the high degree of compactness and shape rigidity in the nanofibers, and resulted in the efficient enzyme immobilization. After immobilization, the esterase enzymes coated on the QDs-nanofibers showed good stability with no loss of enzyme activity even after being recycled for more than ten times. The present study demonstrates the successful application of shape reformable polymeric nanofibers entrapped with QDs for enzyme immobilization for the first time, and so it is anticipated that this technology can be employed in various enzyme applications due to its facile shape control feature in the fabrication of the nanofibers.