Semiconductor nanocrystals (NCs) have been widely researched and reported in the past few years due to their excellent light stability, wide emission persistence and high extinction coefficient. Among them, CdSe NCs are widely used in electronic lighting, solar power generation, photoelectric sensing and other fields. However, the electrical, thermodynamic and photophysical properties of CdSe NCs have a size dependence, crystal surface defects and dangling bonds, and serious biological and environmental toxicity are prone to occur in traditional preparation methods applications, which limit their direct application. To realize the application of quantum dots in various fields, the emission wavelength, size distribution and fluorescence properties of CdSe NCs must be strictly controlled. In this study, monodisperse colloidal luminescent CdSe quantum dots were synthesized by high-temperature thermal injection method, and CdSe NCs were modified with surface ligands, and the effects of ligands with different alkyl chain lengths on the size distribution and fluorescence properties of CdSe NCs were studied. In addition, the spinning solution was prepared by changing the solvent ratio and hybridized with polyvinylpyrrolidone (PVP) to prepare PVP/CdSe QDs hybrid fibers. The results show that the CdSe NCs modified by surface ligands have good stability in the organic solution due to the decrease of intermolecular adsorption the modification of surface ligands, as well as adjustable solubility, which compensate for defects and dangling bonds caused by the decline in fluorescence performance, and play an important regulatory role in the formation of CdSe crystal structure. More importantly, this study combines surface ligand modification and hybridization to improve the adhesion of surface ligands and avoid direct contact between cadmium selenide nanocrystals and the polymer matrix during the preparation of hybrid materials. The fluorophore provides a good microenvironment and ensures the fluorescence performance of CdSe NCs, and the hybrid fiber also has stable fluorescence performance. The introduction of PVP has reduced the biotoxicity and environmental toxicity of CdSe NCs, made the material more environmentally friendly has better biocompatibility, and greatly increased the material’s application range. The experimental results show that PVP/CdSe QDs hybrid microfibers have good hybrid compatibility and dispersion, excellent fluorescence performance and material formability, simple synthesis ways and low cost, and applied to solution processing, optical lighting, Electrode materials, and biological imaging and other fields.