<p>This study reports the fabrication of nanofibers incorporating cholesteric liquid crystals - cholesteryl stearate (CS) and cholesteryl oleyl carbonate (COC) - into a polyacrylonitrile (PAN) matrix using a single-needle electrospinning technique. Structural, optical, and thermal characterizations confirmed the successful integration of liquid crystals without disrupting their intrinsic phase behavior. Polarized optical microscopy (POM) confirmed the preservation of anisotropic optical properties and the alignment of liquid crystal molecules along the fiber axis in both CS/PAN and COC/PAN composites. Scanning electron microscopy (SEM) analysis showed that CS/PAN fibers exhibited a generally bead-free and homogeneous morphology; however, irregular residues of unspun cholesteryl stearate were observed at fiber intersections, likely due to its solid crystalline nature at room temperature. In contrast, COC/PAN fibers displayed elongated bead structures distributed along the fiber axis, yet maintained structural continuity. Moreover, a clear voltage-dependent thinning of COC/PAN fibers was observed, with higher voltages yielding finer fiber diameters. DSC analyses verified the retention of cholesteric phase transitions, including thermal hysteresis, and FTIR spectroscopy indicated molecular-level incorporation of CS and COC into the fibers. These findings demonstrate, for the first time, the successful incorporation of CS and COC into PAN nanofibers via electrospinning. The results underscore the potential of these composites as thermoresponsive and optically active materials. Furthermore, the study reveals that optimizing electrospinning parameters, particularly applied voltage, can significantly enhance fiber uniformity, enabling the fabrication of more homogeneous and structurally stable fibers.</p>