The polyvinylpyrrolidone (PVP) hybrid luminescent micro-/nanofibers doped with the novel hybrid SiO2-coated CdTe nanocrystals (HS-CdTe NCs) have been fabricated for the first time via the electrospinning technique. The morphologies and photoluminescence (PL) emissions of HS-CdTe/PVP micro-/nanofibers prepared by doping the HS-CdTe NCs with the different PL peak wavelength (571, 616, and 643 nm) in PVP fibers were investigated by optical and PL microscope. The results revealed that all the HS-CdTe/PVP hybrid fibers showed an ultralong length for several hundreds of micrometers and a relatively uniform diameter of 1000 similar to 1200 nm. The hybrid fibers displayed a wavelength-tunable PL emission, determining by the PL of doped HS-CdTe NCs. Moreover, similar to the original PL properties of HS-CdTe NCs before the electrospinning, the HS-CdTe/PVP fibers also showed a series of superior PL properties, such as narrow and symmetry PL spectrum, high, and uniform brightness. For comparison purpose, we also prepared three CdTe/PVP hybrid fibers by doping the 553 nm, 600 nm, and 633 nm PL-emitting CdTe NCs respectively in PVP electrospinning fibers. The characterization results showed that, the obtained three CdTe/PVP hybrid fibers had a basically satisfactory micro-/nanofiber morphology with a long length and relatively uniform diameter, but all the fibers exhibited very weak PL emissions. The enormous contrast in PL properties between HS-CdTe/PVP and CdTe/PVP fibers should mainly be ascribed to the different connection modes of ligands with the NCs and the passivation effect of inert hybrid silica shell on HS-CdTe. It is hopeful that the high luminescent HS-CdTe/PVP micro-/nanofibers with the tunable PL peak wavelength would be a good candidate in the optical sensor, light-emitting devices (LEDs), nanometerscale waveguides, and the other related photonic materials. (C) 2014 Elsevier B.V. All rights reserved.